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Field sampling and modelling of creosote-derived contamination in a tidally forced aquifer Bieber, Christine 2003

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Abstract Research into the fate and transport of a creosote-derived groundwater contaminant plume found in an aquifer adjacent to and beneath the Fraser River is presented. The site, located in Coquitlam, B.C., has been an active wood preserving facility since the 1920's. In the source zone, creosote has penetrated into the Fraser Sands aquifer. A capture well has been operated since 1996 to contain and capture the contaminant source. Previous research at the site has demonstrated that the primary component of the dissolved phase plume is naphthalene and that biodegradation of naphthalene is taking place. Suspected terminal electron accepting processes are iron reduction and methanogenesis. High naphthalene concentrations sampled in 1999 despite source containment led to the hypothesis that the plume may be at steady state due to buffering of contaminant concentrations by desorption from aquifer sediments. Naphthalene concentrations sampled in this study show that the contaminant plume is not at steady state. Particle tracking results and sorption data show that the continued presence of high concentrations of naphthalene offshore are likely due to incomplete source containment or to slow migration of contaminants from the onshore region of the plume. Although naphthalene has been the focus of all previous investigations of the offshore plume at this site, recent sampling shows that indane and benzothiophene become the dominant components of the aqueous phase plume towards the discharge point. Relative enrichment of benzothiophene and indane along the plume profile despite these compounds greater susceptibility to tidally-enhanced dispersion proves that observed loss of naphthalene over the plume flowpath is not due to a physical process The results of groundwater flow modelling show that the capture well at the site extends the residence times of contaminants in the aquifer, thereby increasing the opportunity for attenuation of contaminants before discharge to the river. This increase in residence times explains the rapid decrease in naphthalene along the plume flowpath observed in this study. Concentrations of iron and dissolved methane are higher throughout the plume axis than ii in background data collected suggesting that high iron and methane along the plume flowpath are associated with processes specific to the contaminated area. Geochemical modelling shows that degradation of naphthalene at the site may be taking place by iron reduction or a combination of iron reduction and methanogenesis. 111 Table of Contents Abstract i i List of Figures vii List of Tables ix Acknowledgements x 1.0 Introduction 1 1.1 Objective 1 1.2 Overview 1 1.3 Creosote-Derived Contamination 1 1.4 Degradation of Naphthalene 2 1.5 Biomarkers of Anaerobic Naphthalene Degradation 3 1.6 Indane and Benzothiophene 4 1.7 Tidal Forcing 5 1.8 Sorption of Naphthalene 5 2.0 Site Description 7 2.1 Geology and Hydrostratigraphy 7 2.2 Hydrogeology 8 2.3 Site Contamination 9 2.4 Site Geochemistry 11 3.0 Methods 13 3.1 Description of Offshore Profiling System 13 3.2 Description of Offshore Profiling: June 2002 14 3.2.1 Sampling Procedure 15 3.2.2 Analysis 16 3.3 Description of Offshore Profiling: February 2003 17 3.3.1 Sample Collection and Analysis 17 3.4 Soil Sampling 19 3.4.1 Core Collection 19 3.4.2 Organic Carbon Analysis 20 3.4.3 Sorbed Naphthalene 20 4.0 Results and Discussion 21 4.1 Offshore Profiling June 2002 21 4.1.1 Organics 21 4.1.2 Inorganics 22 4.1.3 Dissolved Gases 24 4.1.4 pH, Alkalinity and Conductivity 25 4.1.5 r 4 C-Activity 26 4.1.6 Downgradient Sampling Point 26 4.2 Offshore Profiling February 27 4.2.1 Organics 27 iv 4.2.2 Inorganics 29 4.2.3 Dissolved Gases 30 4.2.4 pH, Alkalinity and Conductivity 32 4.2.5 Metabolic Biomarkers 32 4.3 Offshore Soil Sampling 33 4.3.1 Organic Carbon Analysis 33 4.3.2 Sorbed Naphthalene 34 5.0 Modelling 36 5.1 Groundwater Flow Modelling 36 5.1.1 Introduction 36 5.1.2 Model Domain and Grid 36 5.1.3 Boundary and Initial Conditions 36 5.1.4 Parameter Values 39 5.1.5 Source Containment Wells 39 5.1.6 Calibration 40 5.1.7 Seasonal Variation in Aquifer Gradients 40 5.1.8 Residence Times 41 5.1.9 Implications for Plume Shape 41 5.1.10 Sensitivity Analysis 43 5.2 Geochemical Model 44 5.2.1 Model Objectives 44 5.2.2 Batch Model Design 45 5.2.3 Degradation of Naphthalene by Iron Reduction and Methanogenesis 47 5.2.4 Influence of Degradation on pH and Alkalinity 48 5.2.5 Degradation of Organic Matter 49 5.2.6 Degradation solely by Iron Reduction 50 5.2.7 Mineral Precipitation :.... 51 5.2.8 Surface Complexation 52 5.2.9 Discussion of Limitations 53 6.0 Conclusions 55 6.1 Groundwater Flow 55 6.2 Contaminant Plume 55 6.3 Geochemistry 56 6.4 Recommendations for Further Research 57 References 58 Appendix A : Permits 109 Appendix B: Description of Analyses 118 Appendix C: Organics June 2002 127 Appendix D: Geochemical Data June 2002 132 v Appendix E: Organics February 2003 147 Appendix F: Geochemical Data February 2003 155 Appendix G: Calibration of the Groundwater Flow Model 161 Appendix H : Geochemical Model Input 166 Appendix I: Geochemical Model Output 185 vi List of Figures Figure 2.1.1 Hydrostratigraphy 64 Figure 2.3.1 Site Map 65 Figure 2.3.2 Profiling Results 1996 66 Figure 3.1.1 Profiling System 67 Figure 3.1.2 Sampling System 68 Figure 3.2.1 Profiling Locations June 02 Map View 69 Figure 3.2.2 Profiling Locations June 02 Cross Section 70 Figure 3.3.1 Profiling Locations February 03 Map View 71 Figure 3.3.2 Profiling Locations February 03 Cross Section 72 Figure 3.4.1.1 Coring System (WDPPS) 73 Figure 3.4.2.1 Soil Core Interval Cross Section 74 Figure 4.1.1.1 Maxiumum Naphthalene Concentrations June 2002 75 Figure 4.1.1.2 Naphthalene Concentrations Top: 1996 Bottom: June 2002 76 Figure 4.1.2.1 Iron Concentrations June 2002 77 Figure 4.1.2.2 Nitrate Concentrations June 2002 78 Figure 4.1.2.3 Acetate Concentrations June 2002 79 Figure 4.1.3.1 Dissolved Methane Concentrations June 2002 80 Figure 4.1.4.1 pH June 2002 81 Figure 4.1.4.2 Alkalinity June 2002 82 Figure 4.2.1.1 Maxiumum Naphthalene Concentrations February 2003 83 Figure 4.2.1.2 Naphthalene Concentrations February 2003 84 Figure 4.2.1.3 Indane Concentrations February 2003 85 Figure 4.2.1.4 Ratio of Naphthalene to Indane February 2003 86 vii Figure 4.2.1.5 Benzothiophene Concentrations February 2003 87 Figure 4.2.1.6 Ratio of Naphthalene to Benzothiophene February 2003 88 Figure 4.2.2.1 Iron Concentrations February 2003 89 Figure 4.2.2.2 Acetate Concentrations February 2003 90 Figure 4.2.3.1 Dissolved Methane Concentrations February 2003 91 Figure 4.2.3.2 Dissolved CO2 Concentrations February 2003 92 Figure 5.1.2.1 Model Grid 93 Figure 5.1.3.1 Boundary Conditions 94 Figure 5.1.4.1 Conductivity Zones and River Boundary 95 Figure 5.1.6.1 Seasonal Variation in Flow Directions 96 Figure 5.1.7.1 Particle Tracking Results 97 Figure 5.1.9.1 Sensitivity Analysis: Particle Tracking Results with Low River Gradient 98 Figure 5.1.9.2 Sensitivity Analysis: Particle Tracking Results with High River Gradient 98 Figure 5.1.9.3 Sensitivity Analysis: Particle Tracking Results with Maximum North-South Gradient 99 Figure 5.1.9.4 Sensitivity Analysis: Particle Tracking Results with Minimum North-South Gradient 99 Figure 5.2.2.1 Modelled vs. Field Naphthalene Concentrations using a Half Saturation Constant of 1x10-6 100 Figure 5.2.2.2 Error in fit of modelled to field sampled naphthalene concentrations for half saturation constants between lxlO" 8 and lx l0" 6 100 viii List of Tables Table 3.2.2.1 Suite of aromatic compounds analyzed 101 Table 4.1.1 Maximum Concentrations Sampled June 2002 102 Table 4.1.5.1 Uncontaminated Sampling Location 103 Table 4.2.1 Maximum Concentrations February 2003 104 Table 4.2.5 Concentrations of Organic Compounds at Biomarker Sampling Points. 105 Table 5.1.3.1 Aquifer gradients 105 Table 5.1.3.2 Recharge Rates Input to the Groundwater Flow Model 106 Table 5.1.9.1 Sensitivity Analysis: Summary of Results 106 Table 5.2.2 Batch model initial solution 107 Table 5.2.9.1 Summary of Batch Model Results 108 ix Acknowledgements I would like to thank Roger Beckie for the opportunity to work on this project and for all his guidance along the way. I would also like to thank the other members of my committee, U l i Mayer and Leslie Smith, for their comments, questions, and advice. In addition, I would like to acknowledge the funding of this thesis provided by NSERC in the form of an operating grant to Roger Beckie. I owe huge thanks to Julie-Ann Bouchard and Rich Amos for their contributions in the field portion of this thesis. In addition, I owe thanks to Mario Bianchin, Joshua Caulkins, Randi Williams, and Justin Bieber for their help in the field. Their willingness and enthusiasm to brave the long days were much appreciated. I would also like to acknowledge the hard work of Glenn Budden and the crew of the Ocean Venture for providing the vehicle used during field work and their expertise in its operation. I would like to recognize Maureen Soon for her supervision during the lab analyses that I carried out for this project. I would also like to acknowledge the expertise brought to laboratory analyses carried out by MarianneVandergriendt and Shirley Chatten of the Organic Geochemistry Lab at the University of Waterloo. I would like to thank Willy Zawadzki and Guy Patrick of Golder Associates for generously sharing their data on the site and Myles Parsons of Domtar for authorizing the use of that data. The comments and suggestions I received from everyone in the hydrogroup at U B C throughout my thesis are very much appreciated. In particular, I would like to thank my officemates Yarning Chen and Sharleen Ramos for their company and encouragement. Finally, I am enormously thankful for the support, encouragement, and editing provided by Duane Bieber throughout my pursuit of this degree. I would also like to thank my family and friends for their encouragement. In particular, I am grateful to the Mattmans for always providing a fun and relaxing atmosphere to unwind. x 1.0 Introduction 1.1 Objective The motivation for this research is to understand the fate and transport of a creosote-derived groundwater contaminant plume located adjacent to and beneath the Fraser River. Any explanation of contaminant fate must account for the complex geochemical and biological processes and the tidally-driven groundwater hydrology at the site. Here the results of a field and modelling investigation into these processes are presented. 1.2 Overview The framework for this thesis is as follows. Chapter 1 discusses the results of previous research into the fate and transport of creosote derived contamination, the degradative properties of naphthalene, the anaerobic degradation products of naphthalene, the properties of two persistent creosote-derived compounds, indane and benzothiophene, and finally the effects of tidal forcing and sorption on contaminant distributions and degradation. Chapter 2 of this thesis summarizes the geology and hydrogeology of the site, previously sampled contaminant distributions, and aquifer geochemistry. Chapter 3 describes the methodology applied in field investigations during this study. Chapter 4 provides a discussion of the results of field investigations. Chapter 5 provides documentation and interpretation of the results of groundwater flow and geochemical modelling. The final chapter of this thesis, Chapter 6, summarizes the conclusions of Chapters 4 and 5 and provides recommendations for further research at the site. 1.3 Creosote-Derived Contamination Creosote is the product of the coal tar distillation process and is used as a wood preservative. Because of the widespread historical use of creosote, creosote-derived plumes at wood-preserving facilities are common. Creosote consists of a complex mixture of polycyclic aromatic hydrocarbons (PAHs) (85%), monoaromatic hydrocarbons (MAHs) (10%), and nitrogen, sulphur, and oxygen (NSO) containing heterocyclics (5%) (Mueller et al., 1989). 1 Research into the evolution of creosote plumes has shown that the different components of creosote travel at different speeds in groundwater, with more highly sorbed components moving more slowly and dominating at later times of plume evolution (Fowler, 1994, King and Barker, 1999). Previous research has suggested that when biodegradation is active, concentrations of compounds are expected to increase to steady state, when the rate of supply equals the rate of degradation and then recede as the flux from the source zone changes over time (King et al., 1999). Recent data has shown that this hypothesis may not necessarily be the case for all components (Blaine et al., 2002). As a highly sorbed component of creosote, naphthalene has been identified as a dominant component at later times in plume evolution. 1.4 Degradation of Naphthalene Although naphthalene is readily degraded in aerobic conditions (Mueller, 1989), anaerobic degradation is less well-documented and is generally believed to be slower. Naphthalene degradation under sulphate and nitrate reducing conditions has been observed at a number of sites (Mihelcic and Luthy, 1988, Al-Bashir et al., 1990, Thierrin et al., 1995) yielding naphthalene degradation rates one to two orders of magnitude lower than those reported under aerobic conditions (Rockne and Strand, 1998). Naphthalene degradation under iron-reducing conditions has been documented in the field in some petroleum contaminated aquifers generally in a narrow region at the downgradient edge of the iron-reducing zone (Anderson and Lovley, 1999). Naphthalene degradation by iron reduction at a creosote contaminated site has also been documented using lab microcosms and analysis of electron acceptor utilization, yielding first order degradation rates of between 0.438 and 2.2 yr"1 (Robinson et al., 2001). Recent anaerobic enrichment cultures have demonstrated that complete naphthalene degradation by methanogenesis is also possible where long-term exposure to PAHs exists (Chang et al., 2001). 2 1.5 Biomarkers of Anaerobic Naphthalene Degradation Biomarkers are substances created during degradation of a contaminant. Monitoring of metabolic biomarkers in groundwater provides a direct method of demonstrating in-situ degradation of a contaminant by a particular pathway. Good biomarkers are readily degradable; therefore detection of these substances is indicative only of recent degradation within the plume. In addition, they are not present in uncontaminated waters or already present in the contaminant plume and are specific to the degradative process being investigated. The sequence of metabolic products of anaerobic naphthalene degradation has been identified from lab studies under sulphate-reducing conditions (Annweiller et al., 2002, Zhang et al., 2000). When naphthalene degrades by anaerobic metabolism the following sequence of compounds is created before ring cleavage: 2-naphthoic acid (2-NA), 5,6,7,8-tetra hydro-2-naphthoic acid (TH-2-NA), hexahydro-2-naphthoic acid (HH-2-A), decalin-2-carboxylic acid (D-2-CA). Although these compounds are not usually found in groundwater (Phelps et al., 2002), 2-NA is also a product of aerobic and anaerobic methyl-naphthalene degradation (Annweiler et al., 2002). Methylnaphthoic acid (MNA) is a product of anaerobic degradation of methyl-naphthalene (Sullivan et al., 2001), which has been identified at sites where 2-NA, TH-2-NA and HH-2-A are present. The monitoring of biomarkers to demonstrate degradation in the field has been used to evaluate degradation of alkylbenzenes (Elshahed et al., 2001) and anaerobic naphthalene degradation (Phelps et al., 2002, Gieg and Suflita, 2002). In field and laboratory studies of metabolites produced in degradation of B T E X , field concentrations of metabolites were found to be 3 to 4 orders of magnitude less than concentrations of B T E X (Elshahed et al., 2001). Because concentrations of metabolites are typically so low and degradation rates of many different reactions are involved, sampling of metabolic biomarkers provides only a qualitative indication of current degradation. 3 1.6 Indane and Benzothiophene Considerably less is known about the fate and transport processes involved in the evolution of heterocyclic components of creosote than PAHs, although enrichment in heterocyclics in the water soluble fraction of creosote-derived plumes has been reported (Godsy et al, 1992). Recent research has shown that benzothiophene, which is a sulphur-containing heterocyclic component of creosote, is an inhibitor of naphthalene degradation (Annweiler et al, 2001, Meyer, 2000). Degradation of benzothiophene requires a primary substrate (Dyreborg et al., 1996). Without the presence of a preferred substrate such as phenol, o-cresol, quinoline, or indole, degradation of benzothiophene has been shown to be much slower than degradation of PAHs (Meyer, 2000). Field studies have confirmed a relative enrichment of heterocyclic compounds such as benzothiophene may occur with distance from the source and therefore it has been suggested that they may sometimes behave as non-reactive tracers (Zamfirescu and Grathwohl, 2001). Although degradation of benzothiophene under sulphate-reducing conditions with naphthalene as the primary substrate has been documented (Annweiler et al., 2001), degradation of benzothiophene with naphthalene or methyl-naphthalene as the primary substrate has been observed to occur at a much lower rate than with other substrates (Broholm and Arvin, 2001). Column experiments designed to study the sorption of heterocyclic compounds have found that benzothiophene has a similar retardation to naphthalene in a complex creosote mixture (Broholm et al., 1999). Based on the solubility of benzothiophene which is 130 mg/1 (Pearlman et al., 1984), approximately 3.8 times greater than the solubility of naphthalene, benzothiophene is expected to be sorbed less strongly than naphthalene. Indane is monoaromatic hydrocarbon which has not been the subject of much research. Observations in the field have shown that indane is degradable under anaerobic conditions (Zamfirescu and Grathwohl, 2001). Because the sorption of organic compounds is dominated by hydrophobic interactions, the solubility of these compounds can be used to estimate their affinity to sorb to the soil matrix (Karickhoff, 1984). Based on the solubility of indane which is 108 mg/1, approximately 3.6 times greater than the solubility of naphthalene, indane is expected to be sorbed less strongly than naphthalene. To the knowledge of the author no field or lab-based data on indane sorption exists. 4 Indane and Benzothiophene generally compose 0.3 to 1.5% of creosote by weight (Nylund et al., 1992). Despite their low relative compositions in coal tar creosote, indane and benzothiophene have been identified as prominent contaminants at a site of historical creosote-derived contamination where degradation of other less persistent components has been identified (Zamfirescu and Grathwohl, 2001). Analysis for these two compounds is generally not performed as part of typical contaminated site assessment. 1.7 T i d a l Forc ing Tidal forcing can have significant impacts on the distribution of contaminants in a plume. Diurnal fluctuations in groundwater flows due to tidal forcing increases the dispersion of contaminants (Yim and Mohsen, 1992, Khondaker et al., 1997) and may increase the potential for biodegradation due to increased mixing of nutrients (El-Kadi, 2001). One-dimensional contaminant transport modelling suggests that the large advective and dispersive fluxes caused by tides will produce decreased concentrations onshore adjacent to the tidally forced boundary and consequently increased discharge of contaminants to the boundary will occur (Yim and Mohsen, 1992). This effect wil l be greater where tidal effects are more significant relative to the magnitude of the regional gradient. 1.8 Sorpt ion of Naphthalene Sorption of organic contaminants has been shown to be directly related to organic carbon content in aquifers with content > 0.1 % (Schwartzenbach and Westall, 1981, Karickhoff, 1984). Below 0.1 % organic carbon, attempts to correlate sorption and organic carbon content show mixed results (Maclntyre et al., 1998, Maclntyre and Stauffer, 1991). A long tailing connected with slow desorption has been observed to be associated with low organic carbon materials (Maclntyre et al., 1991). Desorption of contaminants from aquifer sediments has been shown to take place at three time scales. Fast desorption takes place on times scales of hours to days and wil l obey a linear sorption isotherm while slow and very slow desorption which take place on time scales of weeks to years obey a Langmuir-type isotherm (Cornelissen et al. 2000). These 5 desorption resistant fractions may represent the majority of sorbed mass in some sediments due to prolonged contact times and the absence of recent exposure to contaminants (ten Hulscher et al., 2002). A fraction of desorption resistant compounds may also be resistant to biodegradation (White and Alexander, 1996). 6 2.0 Site Description The site that is the focus of this study is located adjacent to the Fraser River in Coquitlam, British Columbia. The site has hosted an active wood preserving facility since the late 1920's. The source of contamination at the site is creosote. Extensive site characterization has been undertaken in the past (Golder, 1997, Golder, 1998) as part of efforts to delineate site contamination. Ffydrostratigraphy and the D N A P L source at the site have been well characterized by boreholes, cone penetrometer tests, and testpits. In addition, the site has been the subject of two university research projects which have focused on the region of the dissolved phase plume located beneath the Fraser River (Anthony, 1998, Bianchin, 2001). A site management plan has been developed to deal with the contamination (Golder, 1999). The following description of the site is summarized from these previous reports. 2.1 Geology and Hydrostratigraphy The geologic setting consists of several hundred metres of recent age glacio-marine, alluvial, swamp and flood plain deposits overlying tertiary sedimentary bedrock (Monahan, 1997). Based on the conceptual model developed by Golder (1997, 1998), the site can be broken up into four hydrostratigraphic units (Figure 2.1.1). The uppermost unit consists of 1 to 2 metres of gravel and silt fill. This near surface fill was originally placed at the site before operations began in the 1920's and since then additional fill has been added as required for site operations. Beneath the near surface fill at the site, clayey silty overbank deposits are present. Thickness of this unit ranges from 3 to 5 metres, with an average thickness of 4.4 metres. The Fraser River Sands aquifer directly underlies overbank deposits at the site. It ranges in thickness from 20.5 to 30.5 metres and has an average thickness of 27 metres. The aquifer is mainly sandy, with sand- silt- gravel- and clay-rich interbeds. The unit underlying the Fraser River Sands is referred to as the Pre-Fraser River Sands. 7 This unit consists of silty, sandy, and gravelly interbeds and is derived from delta slope and/or Pleistocene age sediments. 2.2 Hydrogeology Fraser River water levels in the vicinity of the site vary both seasonally and tidally. Water levels recorded at New Westminster, the hydrographic station located nearest to the site, show that river water levels can vary by up to 1.0 metre seasonally and up to 2.7 metres tidally. Continuous water level monitoring data collected at the site (Golder, 1997, 1998) shows that although the dominant direction of groundwater flow in the aquifer is towards the Fraser River, gradients within the aquifer vary both daily, with tidal fluctuations in river stage, and monthly, with seasonal variations in river stage elevations. In addition to the dominant north-south component of gradients in the aquifer, in the southern region of the site, an east-west component of flow develops. This east-west component of flow is evident in continuous water level monitoring data and in movement of a conservative tracer injected offshore (Bianchin, 2001). The east-west component of flow is due to a combination of an indentation in the shoreline on the western side of the site and the river gradient. The Fraser Sands aquifer is confined by overlying silt and clay overbank deposits. Flow in the aquifer is primarily horizontal, except for the region beneath the Fraser River where a vertical component is present as the aquifer discharges to the river. Pumping test results and tidal analysis have estimated the transmissivity of the aquifer to be between 1 x 10"2 m2/s and 2 x 10"2 m2/s and the storage to be between 4 x 10"3 and 5 x 10"3. Analysis of tidal responses at seven individual site wells yielded estimated 3 2 2 2 transmissivities of between 5x10" m/s and 4 x 10" m/s. The saturated hydraulic conductivity of the silty overbank deposits at the site has been directly measured at 5 x 10"7 m/s. The vertical conductivity of this unit is expected to be 8 higher than this, due to the presence of features such as rootholes, which contribute to secondary porosity. Recharge to the aquifer has been estimated to be approximately 30% of average annual precipitation (Golder, 1997). The percentage of precipitation which infiltrates the aquifer is expected to be greater during the summer months when the water table is lower and shallow flow to drainage ditches at the site will be non-existent, and lower during fall and winter, when shallow groundwater flow in overbank deposits is directed towards drainage ditches. Although losses of infiltrating precipitation to evapotranspiration wil l be greater in summer months than in fall and winter, this effect is considered to be less significant than the effect of shallow flow to drainage ditches during fall and winter (Golder, 1998). Although a greater percentage of precipitation is expected to infiltrate during the summer months, total recharge to the aquifer is greater during winter and fall. 2.3 Site Contamination The source of contamination at the site is a creosote D N A P L plume, which extends into the Fraser sands aquifer to approximately 22 m depth in a small localized area (Fig. 2.3.1). The deep D N A P L source is located approximately 120 metres from the shore of the Fraser River. Borehole and test pit observations used to map the extent of the D N A P L at the site suggest that this is the only area where the N A P L penetrates into the deep zone of the Fraser Sands aquifer, although it extends in the upper region of the aquifer, and in overbank deposits, over a much larger region. As part of the proposed site management plan, a pump and treat program has been in operation since July 1996 to contain the D N A P L source (Golder, 1997). In 1999, the original source containment well, DWW-3, was replaced by well DWW-5, since groundwater modeling showed that better capture of the source could be obtained with a well in this location (Golder, 1999). Further groundwater modelling has shown that the capture zone of this well is at a maximum during low gradient periods and a minimum during periods of high aquifer gradients (Zawadzki et al.,2002). The dissolved phase plume was first mapped from the source zone to where it discharges 9 beneath the Fraser River approximately 200 m downgradient, in 1996 (Anthony, 1998). The depth distribution of the dissolved phase plume corresponds to the depth distribution of the deep D N A P L zone. Because flow in the aquifer is primarily horizontal, the deep D N A P L zone has been inferred to be the primary source of the aqueous phase plume (Golder, 1997). The aqueous plume is composed of PAHs, M A H s and chlorophenols. In 1996, the predominant component of the plume was naphthalene, although other organics such as fluorene, phenanthrene acenaphthene, anthracene, pyrene, fluoranthene, chrysene, benzo(a)pyrene, benzo(b)anthracene, and benzo(b)fluoranthene have also been detected in significant concentrations at the site (Golder, 1997). In 1996, concentrations of naphthalene recorded along the plume axis were found to greatly decrease in the offshore zone of the plume (Fig. 2.3.1). In addition, the ratio of naphthalene concentrations to other PAHs sampled was found to decrease in the offshore zone. Reactive transport modeling (Anthony, 1998) has suggested that significant mass loss must occur in the offshore region of the plume in order to explain the reduced contaminant concentrations found in this zone. Concentrations of methane and dissolved iron along the plume axis suggest that degradation by methanogenesis and iron reduction might explain this loss (Anthony, 1998). The hypothesis that biodegradation of the plume takes place in the offshore region was confirmed by a radiolabeled 14C-naphthalene tracer experiment conducted in 2000 (Bianchin, 2001). Unamended lab microcosms collected in the offshore region of the plume in 1999 also confirmed degradation in this area and predicted an average zero order degradation rate of 1900 pg-f'-yr"1 (Lesser, 2000). Because these microcosms were spiked with high levels of naphthalene, this zero order rate can be interpreted as the maximum rate of degradation (Bekins et al, 1998). Because the products of iron reduction and methanogenesis were not monitored in the field tracer experiment or in the lab microcosms, the degradative pathway of naphthalene attenuation cannot be 10 determined. Despite source containment and confirmed offshore degradation, offshore profiling conducted in 1999 did not demonstrate naphthalene concentrations reduced from 1996 levels. Although inadequate sampling resolution may have been responsible for these results, another possible explanation for this is the buffering of naphthalene concentrations from desorption of naphthalene from the aquifer matrix (Bianchin, 2001). Concentrations of all dissolved contaminants at the discharge point of the plume have been below detection limits when sampled. Because of the magnitude of mass loss near the aquifer river interface, this sharp decrease in concentrations appears to be due to a separate process than that which is responsible for mass loss in the rest of the offshore zone. This decrease in concentrations of dissolved contaminants has been attributed to a change in geochemical conditions and mixing processes in the hyporheic zone (Bianchin, 2001). 2.4 Site Geochemistry Results of profiling in 1996 indicate that groundwater in the contaminant plume is geochemically distinct from downgradient water. Plume groundwater has a lower alkalinity and much lower concentrations of CI, Na, Mg, K , Br, and Sr than water south of the plume. Anthony (1998) suggested that this indicates that downgradient water discharges from the underlying bedrock and silt unit. Profiling of the offshore groundwater plume in 1996 showed that dissolved oxygen levels were low. Anthony (1998) reported dissolved oxygen levels below detection across the site, except in very shallow sampling points located beneath the river where dissolved oxygen levels up to 10 mg/1 were detected. Dissolved oxygen levels up to 3.0 mg/1 were sampled in 1999 (Lesser 2000, Bianchin, 2001). Because of the high levels of dissolved iron present in the aquifer, these high levels of dissolved oxygen were considered geochemically unlikely and were attributed to contamination and interference effects during sampling. 11 Concentrations of nitrate, sulphate, and manganese in the offshore region of the plume have been found to be low. Anthony (1998) reported offshore nitrate concentrations up to 0.3 mg/1, sulphate concentrations up to 1.1 mg/1, and manganese concentrations up to 1.9 mg/1. Profiling in 1999 revealed sulphate concentrations up to 1.1 mg/1, manganese concentrations up to 1.9 mg/1, and nitrate concentrations up to 106 mg/1 (Lesser, 2000, Bianchin, 2001). The higher nitrate values sampled within the plume during profiling in 1999 were considered unrealistically high and attributed to contamination of the samples with nitric acid during collection. During previous profiling events, high iron and methane concentrations have been sampled in the plume core. In 1996, concentrations of up to 63 mg/1 of iron and up to 21.4 mg/1 of methane were sampled. In 1999, iron levels up to 59 mg/1 were sampled. For this reason, iron reduction and methanogenesis are believed to be the dominant terminal electron accepting processes at the site. Anthony (1998) found that the pH of onshore groundwater was 6.2 +1-2. Lesser (2000) reported pHs between 5.6 and 6.9 at 8 depth intervals between 0.5 and 15 m below the aquifer river interface at a sampling location offshore along the plume axis. Because iron reduction and methanogenesis will have opposing effects on pH, monitoring this parameter along the plume profile may help constrain these processes. 12 3.0 Methods A n environmental review by the Fraser River Estuary Management Program (FREMP) and approval for temporary work from the Fraser River Port Authority (FRPA) were obtained prior to commencement of offshore profiling work. Copies of the permits obtained are provided in Appendix A. As with all previous groundwater sampling efforts in the offshore region of the plume (Anthony, 1998, Bianchin, 2001), the Waterloo Drive Point Profiler (Pitken, 1994) was used to obtain groundwater samples representative of discrete depth intervals over several vertical profiles. The profiling system was deployed from a 22 metre seiner (salmon fishing boat) with 5 point anchoring capability. The profiler was advanced using a pneumatic hammer suspended from the seiner's boom. The coordinates of groundwater sampling points were determined by triangulation. In the first round of sampling, measurements of distances to nearby dolphins, which are normally used for anchoring log booms, were used. Because dolphins situated offshore tend to rot and often disappear during the spring freshet, in the second round of profiling, more permanent survey points installed onshore were used for triangulation. Accurate depths of groundwater sampling locations were determined by using a water gauge to record tidal fluctuations of water levels during the course of sampling and relating water level fluctuations to the initial depth of water when profiling began. 3.1 Description of Offshore Profiling System A diagram of the profiling system used is included in Fig. 3.1.1. The profiler tip is equipped with six 0.6 mm diameter screened ports, which are connected to a common reservoir. The profiling tip is connected to the pneumatic hammer using 1.5 metre lengths of A W drill rod. As the profiling tip is advanced, extra lengths of drill rod are added as needed. Teflon-lined tubing runs inside the drill rods, connecting the port reservoir to the sampling system on the deck of the seiner. The sampling system consists of a sampling manifold, peristaltic pump, and flow through cell (Fig. 3.1.2). The sampling manifold consists of 2 sampling heads, a three way valve, and a pressure gauge. 13 The sampling heads accommodate 40 ml glass vials. The peristaltic pump is connected between the sampling manifold and the flow through cell. The flow-through cell is a glass cell equipped with pH, temperature, and conductivity probes. To collect a sample, the profiler is first driven to the desired sampling depth. Next, a minimum of three pore volumes is purged from the system. Purging continues until parameters monitored in the flow-through cell have stabilized. To prevent clogging of the sampling ports, distilled water is pumped into the aquifer as the profiler tip is advanced. When the desired depth for sampling is reached, the direction of flow is reversed. To minimize cross contamination between profiling locations, one system volume of methanol is flushed down through the system and pumped back up. 3.2 Description of Profiling: June 2002 Initial profiling of the plume was performed from June 9 t h to 13 t h, 2002. Five profiling locations, ranging from approximately 30 to 60 metres offshore, were sampled along the axis of the plume (Figure 3.2.1). Between 5 and 11 discrete interval groundwater samples were taken at each profiling location (Figure 3.2.2). In addition, one profiling location (R02-7) approximately 500 metres downstream was sampled. 5 discrete interval samples were collected at this location. This profiling location was selected as representative of geochemical conditions in uncontaminated groundwater in an interval of the Fraser Sands aquifer similar to the interval from which the samples within the plume were collected. This profiling took place during a period of high water levels in the Fraser River and correspondingly lower average aquifer gradients directed towards the river. Based on hourly river elevation data recorded at New Westminster, which is the hydrographic station nearest to the site, the average river water level over the period of sampling was 1.28 metres above mean sea level (amsl). During sampling, the river water level recorded at New Westminster varied by up to 1.81 metres in a single day, due to tidal fluctuations 14 3.2.1 Sampling procedure Prior to sample collection, a minimum of three pore volumes were purged from the system. After three pore volumes had been purged, purging continued until the parameters monitored in the flow through cell had stabilized. The parameters collected in the flow through cell were then recorded. Samples to be analyzed for dissolved gases and volatile and semi-volatile aromatic hydrocarbons were collected in an anoxic environment using a sampling manifold. They were subsequently stored on ice to limit post-sampling microbial alteration. Samples were collected in 40 ml glass screw top bottles with a Teflon lined septa. Samples to be analyzed for aromatic hydrocarbons were preserved with 0.4 ml of 10% sodium azide solution. Samples to be analyzed for cations and anions were filtered using a 0.45 um polysuppor filter and collected in 60 ml polyethylene bottles. Samples allocated for anion analysis were frozen until analysis. Samples allocated for cations analysis were acidified with nitric acid to pH 2 and kept on ice until analysis. Alkalinity was determined onsite by titration using the indicator bromocresol green/methyl red. A micropipet was used to add 0.1 N H C l to a 25 ml aqueous sample until change in colour marked the end point of the titration. Samples to be analyzed for 1 4C-activity were also collected during this profiling round. Because the 14C-naphthalene tracer injected in 2000 was observed to move very little during the 230 days after injection during which it was monitored (Bianchin, 2001), samples were collected to assess the possibility that measurable concentrations of 1 4 C -naphthalene were still present in the aquifer. Samples to be analyzed for 1 4C-activity were collected in 40 ml glass bottles with Teflon-lined septa, preserved with 0.4 ml of 10 M NaOH, and kept on ice until analysis. 15 3.2.2 Analysis Analysis for the polycyclic aromatic components of creosote was performed at the University of Waterloo Organic Geochemistry Laboratory. Samples were solvent extracted, and a gas chromatograph equipped with a flame ionization detector was used to determine concentrations of 21 compounds (Table 3.2.2.1). A detailed description of the procedure used is included in Appendix B. Analysis for dissolved methane and carbon dioxide was performed using a gas chromatograph (GC-8A Shimadzu) by a method modified from Anthony (1998). 4 ml of Argon, the carrier gas of the GC, was added to each sample while 4 ml of sample water was simultaneously removed from the vial to maintain atmospheric pressure. The vial was then shaken at room temperature for 5 minutes to allow the liquid and gas phases within the vial to equilibrate. 0.4 ml of the gas phase within the vial was then removed and injected into the GC. The average temperature of the vials after shaking was 15 °C. A detailed description of dissolved gases analysis is included in Appendix B. Analysis for cations was performed using inductively coupled plasma - optical emission spectroscopy (ICP-OES EPA Method 601 OB) at A L S Environmental, Vancouver, British Columbia. Analysis for anions was performed using an ion chromatograph (IC) (Dionex DX-100). The IC was calibrated to analyze for concentrations of bromide, acetate, chloride, sulphate, nitrate, and phosphate. To evaluate the possibility of significant concentrations of the radiolabeled naphthalene tracer injected in February 2000 (Bianchin, 2001) persisting near the injection location, total 1 4C-activity was evaluated in the samples considered most likely to have encountered the tracer based on previous mapping of the tracer plume. 15 mL of scintillation cocktail (Ecolume, ICN) was added to 5 mL of each sample analyzed. Vials were subsequently stored in the dark for 48 hours before being quantified using a scintillation counter (Beekman LS 6500). Scintillation counting was performed until statistically less than 2% error had been achieved, or until a maximum counting time of 10 hours had been reached. A l l 1 4 C radioactivity analyses were performed in duplicate. 16 3.3 Description of Offshore Profiling: February 2003 To assess the effect of seasonal variations in aquifer gradients on the distribution of concentrations in the plume, profiling was conducted from February 9 t h to 12 t h, 2003. This profiling took place during a period of lower water levels in the Fraser River and correspondingly higher average aquifer gradients directed towards the river. Hourly river elevation data recorded at New Westminster, the hydrographic station nearest to the site, shows that the average river water level over the period of sampling was 0.3 metres above mean sea level (amsl), approximately one metre lower than during June sampling. During sampling, the river water level recorded at New Westminster varied by up to 2.2 metres in a single day, due to tidal fluctuations. This fluctuation is approximately 0.4 metres greater than that observed in June 2002. In this round of sampling, 6 locations along the plume axis ranging from approximately 23 to 45 metres offshore were profiled (Figure 3.3.1). Between 5 and 9 discrete interval groundwater samples were taken at each profiling point (Figure 3.3.2). 3.3.1 Sample Collection and Analysis Benzo(b)thiophene and indane, two compounds that had been identified as dominant in the last sampling round, but had not been previously analyzed for concentrations, were analyzed with all other aromatic compounds at the Waterloo Organic Geochemistry lab. Dissolved gases were analyzed onsite using a GC (Varian CP-4900). A 125 ml Erlenmeyer flask equipped with a rubber stopper with openings for an inflow tube, outflow tube, and a rubber septa was filled directly from the peristaltic pump until no air bubbles remained in the flask. Sample water was then continuously flushed through the flask for 5 minutes. At the end of 5 minutes, the flask was turned upside down and a rubber septa was inserted. With the inflow and outflow tubes still open, 40 ml of Helium, the carrier gas of the GC, was injected into the flask. The inflow and outflow tubes were then immediately closed off. The flask was then shaken for 10 minutes. At the end of 10 minutes, the flask was turned right side up and 10 ml of the gas phase in the flask was withdrawn and injected into the GC. 17 To correct for atmospheric contamination of the dissolved gases data, dissolved oxygen was analyzed using the 0 to 1 ppm range and 1 to 12 ppm range dissolved oxygen CHEMets kits. These methods utilize the Rhodazine D method and the indigo carmine method. Concentrations of the metabolic biomarkers of naphthalene were analyzed during this round of sampling. Samples were collected and analyzed following the technique developed by Phelps et al. (2002) to determine the concentrations of metabolites formed by the anaerobic degradation of naphthalene. Samples were collected in 3.8 L amber glass bottles and acidified to pH 2 before being shipped on ice to the University of Waterloo Organic geochemistry lab for analysis. A detailed description of the analysis is included in Appendix B. Samples collected to be analyzed for cations were analyzed only for iron, as this was the dominant cation identified by ICP-OES during sampling in June 2002. Samples were analyzed for total iron using a H A C H DR/2400 spectrophotometer. The analysis made use of the Phenanthroline method (HACH Method 8146), which is designed to analyze for ferrous iron. Prior to analysis with the Phenanthroline method, all ferric iron in the sample was reduced to ferrous iron by adding 105 pi of hydroxamine hydrochloride to 1 ml of sample and waiting 10 minutes for reduction to occur. Samples were diluted by a factor of 25 to reduce concentrations to within the limits of the phenanthroline method. A l l other aspects of sample collection and analysis were performed identically during the June 2002 and February 2003 sampling events. 18 3.4 Soil Sampling 3.4.1 Core Collection During the initial field work performed in June 2002, the Waterloo Drive Point Piston Sampler (WDPPS) (Starr and Ingleton, 1992) was used to obtain soil core samples both inside the plume and at a point downstream from the plume, which was considered to be representative of similar uncontaminated soils. The WDPPS is a direct push instrument well suited to taking shallow (6 to 9 metres) soil core samples in sand, silt and soft clays. The advantage of this instrument at contaminated sites is that samples can be collected at depth without sampling soils above the interval of interest, thereby reducing the possibility of contamination of the soil sample by overlying soils. A diagram of the WDPPS system is provided in Fig. 3.4.1.1. The WDPPS consists of an inner rod connected to the drive point and an outer shell, which is lined with the sampling tube. As the profiler is advanced to the sampling interval, extra inner and outer rods are added as needed. At the interval to be sampled, the inner rod is secured in place while the outer shell containing the sampling tube is advanced. Once the sampling tube has been advanced by one rod length, the entire sampling system is withdrawn. In this sampling investigation, the WDPPS system was driven by the same mechanism as was used in groundwater profiling; a pneumatic hammer suspended from the ship's 25 ton boom. Using the WDPPS on the river presented challenges not faced on land. Once a core had been collected and the system was removed from the soil at the river bottom, care was taken to minimize the time that the core was submerged in the river. Sample loss would have occurred i f the sample was left submerged in free water. After the cores were collected, their ends were cut off with a hack saw. The cores were then sealed with polyethylene caps lined with Teflon tape to minimize sorption, and the ends of the cores were dipped in wax and duct taped. Core samples were frozen within 24 hours of collection. 19 3.4.2 Organic Carbon Analysis Organic Carbon was analyzed on soil samples collected from two cores. Core 1 (C02-1) was collected along the plume axis from a depth of 7.8 to 8.8 metres below the bottom of the river bed (Fig. 3.4.2.1). Core 2 (C02-2) was collected downstream, outside of the plume and at a comparable distance offshore, from a depth 5.3 to 6.1 metres below the river bed. Sediments collected in both cores consisted of coarse to medium sand. Representative samples for organic and inorganic carbon analysis were obtained by homogenizing subsamples collected at several depth intervals along the cores. These samples were dried overnight at between 50 and 60 °C. Once samples were dry, an automatic grinder was used to grind the samples into a fine powder. Samples were analyzed for inorganic carbon using a CM5130 UIC Inc. coulometer. Samples were analyzed for organic carbon using a Carlo Erba NA-1500 Analyzer (Verardo et al., 1990). 3.4.3 Sorbed Naphthalene Soxhlet extractions (Bouchard, 2003) to estimate sorption of naphthalene to the soil were performed on each of the same soil core intervals used for organic carbon analysis. The extracted solvent was analyzed for naphthalene using a gas chromatograph/mass spectrometer (GC/MS). For more detail on the soxhlet extractions and analysis of the solvent refer to Bouchard (2003). 20 4.0 Results and Discussion 4.1 Offshore Profiling June 2002 Sampling in June 2002 focused on the region of the plume previously identified as an active zone of biodegradation (Anthony, 1998, Bianchin, 2001). Profiling points along the cross section A - A ' were selected to investigate how concentrations of organic compounds and geochemical conditions vary along the flowpath of the plume. 4.1.1 Organics Naphthalene concentrations observed along the cross section A - A ' (Figure 4.1.1.1, Figure 4.1.1.2) are significantly lower than concentrations observed in 1996. Because this sampling round included detailed data collection in a region over which concentrations were previously interpolated rather than directly sampled, the amount of attenuation over the entire flow path cannot be accurately constrained. Instead, concentrations sampled in this round can be directly compared to concentrations sampled previously at specific locations. For example, concentrations at sampling point R96-5 have decreased from 166 pg/1 to 5 pg/1 between 1996 and 2002. Although naphthalene was previously identified as the dominant contaminant in the offshore region of the plume, two contaminants that were not within the suite of volatile aromatic compounds analyzed, indane and benzothiophene, were the most prominent components observed in this sampling round. Because these compounds have not been previously identified in the onshore or offshore regions of the plume, they were not anticipated and the GC was not calibrated to analyze for them. Although the concentrations were not determined, these compounds were found to have the two most prominent peaks on the GC chromatogram for most samples. Concentrations of all other creosote compounds analyzed were low. Concentrations of 1-methyl naphthalene up to 86 pg/1 were sampled during this round. Maxiumum concentrations of biphenyl, acenaphthylene, acenaphthene, flourene, dibenzofuran, and phenanthrene were below 35 pg/1 at all profiling locations (Table 4.1.1). Complete results of these analyses are available in Appendix C. 21 4.1.2 Inorganics Iron concentrations sampled along the plume axis during this round vary between 21 and 112 mg/1. In this round of sampling, the greatest iron concentrations are observed in R02-2, the profiling point containing the most naphthalene, and in two shallow sampling intervals (Figure 4.1.2.1). The high iron concentrations measured at shallow sampling intervals are consistent with data collected in 1999. These higher iron concentrations in shallow intervals are likely due to degradation of organic matter by iron reduction. Anthony (1998) reported dissolved iron concentrations increasing along the plume profile. Data collected in this study suggests that increasing dissolved iron concentrations sampled along the plume flowpath in 1996 may have been due to increasing degradation of organic matter closer to the river bottom, rather than degradation of naphthalene. In this profiling round, nitrate concentrations up to 7 mg/1 were sampled (Figure 4.1.2.2). In samples with higher naphthalene concentrations, nitrate values up to 2.7 mg/1 were observed. Although high nitrate concentrations are not commonly observed in waters with high iron and methane, these nitrate concentrations are geochemically plausible, as the reduction of nitrate by ferrous iron is a slow process without the presence of a catalyst such as Cu(II), Sn(II) or Ag(I) (Ottley et al, 1997). In addition, laboratory microcosm studies have shown that biodegradation of phenols may occur by concurrent nitrate and iron(III) reduction (Broholm et al., 2000). Nitrate reduction has been shown to inhibit methanogenesis although the presence of nitrate does not (Clarens et al., 1998, Percheron, et al., 1999). Recent research suggests that methane oxidation by nitrate is unlikely as nitrate may be toxic to methane-oxidizing bacteria (Wang and Ineson. 2003). The possibility that higher nitrate values sampled during this round may be the result of the mixing of plume water with higher nitrate water downgradient of the plume and in the river was considered. During the spring freshet, aquifer gradients directed towards the river are at a minimum, and therefore the influence of the pumping well at the site is at a maximum. During this period of time, aquifer gradients beneath the river may reverse and water from the river and downgradient may infiltrate the aquifer. The influence of 22 the large advective and dispersive fluxes caused by tides may result in increased mixing of nutrients between the aquifer and these waters. This hypothesis would explain high nitrate values in the low naphthalene water found at deeper intervals and intervals closer to the discharge point. However, the high nitrate concentrations found at sampling intervals containing high naphthalene water are more difficult to explain. The presence of naphthalene in these samples indicates that this water must be from the source area. In addition, this water is more than 20 metres from the discharge point. The possibility of mixing of waters over 20 metres from the discharge point is unlikely. For this reason, the contamination of samples with the nitric acid used for preservation of other inorganic samples is a more likely explanation of the high nitrate values recorded in the plume core. Because both sampling rounds which have taken place during the freshet season have resulted in high nitrate concentrations, future sampling should closely monitor this parameter to confirm that nitrate does not infiltrate the aquifer during the freshet season. Concentrations of SO42" and M n 2 + are low throughout the area sampled. This suggests that they are not involved in electron transfer processes at the site. This is consistent with all previous sampling results (Anthony, 1998, Bianchin, 2001, Lesser, 2000). Acetate concentrations over the area sampled ranged from below detection to 253 uM, but over the majority of the area sampled, acetate concentrations averaged 20 u M (Figure 4.1.2.3). Elevated acetate concentrations were observed in two sampling depths at profiling location R02-2, which contained the greatest concentrations of naphthalene observed in this round of sampling. The level of acetate in an aquifer is an indicator of the terminal electron accepting process (TEAP). When Fe(III) reduction is active, and not limited by availability, acetate and dissolved hydrogen levels will be too low for sulphate reduction or methanogenesis to occur (Lovley and Chapelle, 1995). Acetate concentrations are typically between 0 and 6 uM in iron reducing environments and between 2 and 50 u M in sulphate reducing environments (Albrechtsen et al., 1999 and references therein). When geochemical 23 conditions are not at steady state, more than one TEAP may be active (Lovley and Chapelle, 1995). The levels of acetate observed at this site are greater than those typically observed in iron reducing environments suggesting that methanogenic conditions with limited Fe(III) reduction exist within the aquifer. Bromide concentrations were low throughout the area profiled. This indicates that either the injected bromide tracer (Bianchin, 2001) has migrated outside of the region profiled or concentrations have been reduced below detection by dispersion. Modelling results presented in Chapter 5 suggest that migration of the tracer outside of the region sampled is more likely. Chloride levels vary from 2.3 to 333 mg/1 over the area profiled (Figure 4.1.2.7). Concentrations are greater by an order of magnitude in the deepest sampling points, indicating that water sampled at these profiling points originates from a different source than water in the plume. Anthony (1998) suggested that this water is most likely associated with the underlying lower bedrock and sandy silt, since the river is a regional discharge area. Phosphate was not detected in any of the samples analyzed during this round of sampling. This is consistent with all previous sampling results (Anthony, 1998, Bianchin, 2001, Lesser, 2000). 4.1.3 Dissolved Gases Concentrations of dissolved methane range from 0.4 to 10.7 mg/1 over the area profiled (Figure 4.1.3.1). The higher methane concentrations were generally found in deeper sampling points and towards the discharge point of the plume. High dissolved methane concentrations were also found in the depth interval with the greatest naphthalene concentration. Dissolved methane concentrations sampled in 1996 were higher in water underlying the plume. This is consistent with data sampled in this round as high dissolved methane was found in deeper sampling points. Dissolved CO2 concentrations were below detection in the majority of groundwater 24 samples. In samples where dissolved CO2 was detected, aqueous concentrations ranged from 39 to 129 mg/1. The lack of detectable amounts of C 0 2 in most samples is likely due to the low partial pressures of CO2 in the samples. This result suggests that the detection limit of the method of analysis used in this round is too high to provide useful information about the dissolved CO2 concentrations in this aquifer. Small CO2 peaks observed on the GC chromatogram confirm this hypothesis. Because pH and alkalinity data were collected, the concentration of dissolved CO2 can be predicted using the code Phreeqc by Parkhurst and Appelo (1999). These speciation calculations assume that carbonate geochemistry is at equilibrium. Dissolved CO2 concentrations predicted by these speciation calculations are consistently higher than measured dissolved CO2 concentrations. Where measured CO2 concentrations are above detection, measured CO2 concentrations are up to 189 mg/1 less than predicted concentrations. This difference in CO2 concentrations may in part be due to the sensitivity of speciation modeling to small changes in pH over the range of pH encountered in most samples. Many samples have pH very near 6.4. In this region of pH, small errors in pH lead to large errors in predicted dissolved CO2 concentrations. For example, for sample R02-3-4 a change in pH from 6.4 to 6.5 results in a change in predicted dissolved C 0 2 of 121 mg/1. Lower measured CO2 concentrations may also be due to degassing of CO2 during sampling. A comparison of measured and calculated dissolved CO2 concentrations is included in Appendix D. 4.1.4 pH, Alkalinity and Conductivity pH values within the plume range from 6.07 to 7.66 (Figure 4.1.4.1). Generally, lower pH values were observed in the northern, or upgradient, region of the area profiled. At all points profiled, the highest pH values were observed in the deepest intervals sampled. pH values in the offshore region of the plume have not previously been profiled with a flow through apparatus. Anthony (1998) stated that the pH of the inland groundwater was found to be 6.2 +1-2. Lesser (2001) reported pHs between 6.0 and 7.0 offshore, but did not use a flow through apparatus to obtain these values. Alkalinity values observed in this round of sampling range from 3.1 to 13.0 meq/1 (Figure 25 4.1.4.2). The alkalinities of contaminated water samples range from 4 to 6 meq/1. Conductivity values ranged between 150 and 500 pS/cm throughout most of the area profiled. Conductivities greater by an order of magnitude were observed in the deepest intervals sampled. This indicates that a zone of distinctly different water, with higher total dissolved solids (TDS), is present in the deepest regions of the aquifer. This data provides further evidence of the presence of water derived from regional discharge in the deep region of the aquifer beneath the plume. High calcium and chloride concentrations observed in the deepest points profiled support this hypothesis. 4.1.5 14C-activity Six samples were analyzed for total 1 4C-activity. Samples were chosen for analysis based on their probability of having encountered the radioactive tracer. One sample, from the downgradient sampling location, was selected for analysis to provide an estimate of background 1 4C-activity. The sampling location that had the greatest naphthalene concentration and was closest to the injection interval had the greatest activity of all samples, but the increase in activity of this sample over the background activity was low. For this reason, further analyses for 14C-naphthalene and 1 4 C-C02 , as performed during monitoring of the tracer plume (Bianchin, 2001, Lesser, 2000), were not carried out. Complete results of 1 4C-activity analyses are included in Appendix D. 4.1.6 Downgradient Sampling Point Sampling point R02-7 is located approximately 500 metres downgradient of the plume axis. Although a sampling point closer to the plume axis, but still outside of the 5 ppb contour, would have been preferable, log boom storage downstream of the plume axis made this impossible. To ensure that samples collected at sampling location R02-7 were representative of the geochemical conditions in uncontaminated offshore waters, all samples collected at this point were analyzed for creosote-derived compounds. Of the suite of 21 compounds 26 which were analyzed, none were detected at this sampling location. Indane and benzothiophene were also not detected at this location. Bromide, sulphate, phosphate, and nitrate concentrations are also all below detection in the intervals sampled at this location. pHs ranged from 6.8 to 7.6 and alkalinity ranged from 3.1 to 4.8 meq/1. These pH and alkalinity values are within the range of alkalinity and pH observed within the plume. Complete data for this location is displayed in Table 4.1.5.1. Analysis for cations by ICP-OES was only performed on one sampling interval at this location at 13.28 metres depth. In that sample, iron was present at 16 mg/1. This concentration of iron is lower than any iron concentration sampled along the plume axis. This low iron concentration suggests that higher iron concentrations in contaminated samples may be due to biodegradation of contaminants by iron reduction, but because only one sample for dissolved iron was analyzed it could be possibly be that higher iron groundwater over or underlies this sampling interval. Dissolved methane concentrations sampled at this profiling point range from below detection to 1.2 mg/1. These values are considerably lower than the dissolved methane concentrations in the plume. This data suggests that methanogenesis may be a significant process in the plume. 4.2 Offshore Profiling February 2003 4.2.1 Organics Offshore profiling to examine the effect of seasonal variation in river stage elevation and changes in the capture zone of the source containment well at the site took place from February 9 t h to 12 t h, 2003. Six locations along the plume axis were profiled. In this round of sampling, profiling focused on obtaining data as close to shore as possible, since profiling in June 2002 had shown reduced contaminant concentrations closer to the former discharge point of the plume. Between this round of sampling and the last round, one of the dolphins that had been 27 used for determining the coordinates of sampling points and for aligning the sampling points along the cross section rotted away. For this reason, two survey locations on shore were used for positioning rather than dolphins. Because the dolphin which had previously been used for alignment of profiling locations had rotted away, in this round, profiling locations were situated up to 15 m east of the axis previously profiled. Because of the shape of the plume contours and the scale of the plume established during previous sampling, this amount of offset is not considered to be a significant influence on the correlation of the data. In addition, profiling points R03-1 and R03-2 are similar distances offshore, while R03-1 is situated along the initial axis profiled and R03-2 is located 14 metres east of R03-1. Data collected from these two locations show a high degree of correlation. This further suggests that error due to the offset of profiling points is minimal. The results of this round of profiling confirm the reduction in offshore naphthalene concentrations observed between sampling in 1996 and 1999 and recent sampling (Figure 4.2.1.1). Naphthalene concentrations sampled in this round are displayed along cross section A - A ' in Figure 4.2.1.2. Indane concentrations up to 873 u.g/1 were sampled in this round of profiling (Figure 4.2.1.3). Although maximum indane concentrations are lower than maximum naphthalene concentrations, indane levels at the sampling locations closest to the discharge point were up to 348 pg/1. This data suggests that significant concentrations of indane may be discharging to the river. A plot of the ratio of naphthalene to indane sampled shows the relative enrichment of indane along the flowpath (Figure 4.2.1.4). This suggests that naphthalene is subject to attenuation processes that indane is not. Benzothiophene levels of up to 140 u.g/1 were sampled (Figure 4.2.1.5) and levels of up to 55 u.g/1 were sampled closest to the discharge point of the plume. A plot of naphthalene versus benzothiophene concentrations over the region profiled show the enrichment of benzothiophene along the flowpath (Figure 4.2.1.6). Because indane and benzothiophene have higher solubilities and lower K o W than 28 naphthalene (Pearlman et al., 1984), they are expected to experience lower sorption to aquifer sediments. They will therefore travel at higher velocities in groundwater and will be more susceptible to mass loss due to dispersion. The enrichment of indane and benzothiophene relative to naphthalene suggests that mass loss of naphthalene is due to chemical and biological processes. Although benzothiophene and indane are expected to be preferentially released from the N A P L source due to their higher solubilities, because the scale and age of the source is much greater than the expected travel time between sampling points, the effect of changing fluxes from the source zone is not expected to have a significant impact on ratios of indane and benzothiophene to naphthalene over the flowpath. Concentrations of 1-methyl naphthalene up to 138 pg/1 were sampled during this round. The highest concentrations of 1-methyl naphthalene were sampled in points R03-6 and R03-1. The high concentration sampled in R03-1 is poorly correlated with all other data collected in this profiling round and in June 2002. The poor correlation between point R03-1 and other data suggests that the distribution of 1-methyl naphthalene is more heterogeneous than the distribution of other contaminants. Concentrations of all other creosote compounds analyzed were low. Maximum concentrations of biphenyl, acenaphthylene, acenaphthene, fluorene, dibenzofuran, and phenanthrene were below 45 pg/1 at all profiling locations (Table 4.2.1). This is consistent with sampling performed in June 2002. 4.2.2 Inorganics Iron concentrations sampled along the plume axis during this round varied between 23 and 95 mg/1. The greatest iron concentrations were observed at the more highly contaminated sampling location and in the two shallowest sampling intervals (Figure 4.2.2.1). Nitrate levels of up to 0.4 mg/1 were observed in this sampling round. This is consistent with the sampling of the plume by Anthony (1998) under higher gradients due to lower 29 river stage elevation. Nitrate levels observed in this sampling round are lower than those observed in June 2002 sampling. Concentrations of sulphate, bromide, chloride, and phosphate were found to be consistent with values obtained from profiling in June 2002. Results are displayed in Appendix F Samples were not analyzed for dissolved manganese(II) in this sampling round, but since values were low in all previous sampling, dissolved manganese is not likely to be involved in electron transfer. Acetate concentrations ranged from below detection to 47 u M (Figure 4.2.2.2) over the area sampled. Overall acetate concentrations are consistent with June 2002 levels. 4.2.3 Dissolved Gases Because of the presence of high amounts of dissolved iron in the aquifer, dissolved oxygen levels were expected to be low or below detection. Although this was the case for the majority of sampling intervals, four sampling intervals had dissolved oxygen levels above .5 mg/1. Duplicate samples at these intervals confirmed that these higher oxygen readings were not the result of contamination. Because the possibility of oxygen existing in high iron waters is geochemically unlikely, these higher oxygen values are likely due to interference. The presence of significant levels of ferric iron in a sample will interfere with the Rhodozine D and indigo carmine indicator methods used in the Chemets kits (White et al., 1990). Because these indicator methods involve a redox reaction, the presence of an easily reduced species such as ferric iron will cause inaccurately high dissolved oxygen readings. For this reason, data obtained from Chemets kits could not be used to correct for atmospheric contamination in dissolved gas data obtained using the GC. Instead, 0 mg/1 of dissolved oxygen was assumed for all sampling points, because of the high concentrations of ferrous iron present in the aquifer. Data obtained using the GC was corrected with this assumption. This correction on average changed recorded methane levels by 0.7 mg/1 and CO2 levels by 5.5 mg/1. These changes correspond to an average correction of 5.7%. The maximum correction made was 21.6%. 30 Dissolved methane concentrations observed in this round were between 5 and 22 mg/1 (Figure 4.2.3.1). These concentrations increase towards the discharge point, which is consistent with the dissolved methane concentrations observed in June 2002 and previous sampling (Anthony, 1998). On average, dissolved methane levels observed in this round are greater than levels observed during June 2002 sampling. The difference in dissolved methane concentrations between the two sampling rounds could be due to differences in the analysis techniques used as samples collected in the first round of sampling are likely more susceptible to degassing of methane and CO2 during collection. Transportation and storage of samples before analysis may also have affected dissolved gas concentrations observed in June 2002. Dissolved CO2 concentrations observed in this round ranged from 37 to 198 mg/1 (Figure 4.2.3.2). This data shows much greater consistency than June 2002 dissolved CO2 concentrations. This improved consistency is most likely a result of the lower detection limit of the method of analysis used in this round, since the partial pressures of CO2 sampled were generally lower than 0.05. The greatest dissolved CO2 concentrations sampled in this round were in the shallowest sampling intervals. This result suggests that the increasing concentrations of CO2, which Anthony (1996) attributed to degradation of naphthalene, are more likely associated with increased degradation of organic matter closer to the river aquifer interface. Dissolved organic carbon measurements along the plume profile would confirm this hypothesis. Dissolved C 0 2 concentrations predicted by speciation modeling are consistently greater than measured concentrations. Similar to sampling in June 2002, this inconsistency can be explained by a small negative bias in pH measurements. Error in alkalinity and temperature data may also affect predictions of dissolved CO2. A comparison of measured and calculated dissolved CO2 concentrations is included in Appendix F. 31 4.2.4 pH, Alkalinity and Conductivity pH, alkalinity, and conductivity values are consistent with values obtained from profiling in June 2002. Results are displayed in Appendix F. 4.2.5 Metabolic Biomarkers Two aqueous groundwater samples were collected in the region of the aquifer beneath the Fraser River. Samples R02-5-4 and R02-6-3 were collected at depths of 8.8 and 7.5 metres below the river bottom, respectively. The two samples were collected approximately 1.5 metres apart along the flowpath of the plume. 2-NA was not detected in either of the samples collected and analyzed for metabolic biomarkers. A small amount of M N A (< 2 pg/1) was detected in the second duplicate of both samples. Spectrum matches for TH-2-NA, HH-2-NA, and OH-2-NA were found in both duplicates of each sample. Retention times of TH-2-NA and HH-2-NA obtained by Craig Phelps (Pers. Comm.) were used to determine i f the matching spectra matched the compounds of interest. One of the matching spectra from TH-2-NA has a retention time very close to that obtained by Phelps et al. (2002). Results of the analysis of groundwater samples for organics at R03-6-3 and R03-5-4 are summarized in Table 4.2.5. Because a P A H sample was not obtained at sampling point R03-5-4, a linear interpolation of concentrations sampled immediately above and below this interval was used to determine concentrations at this point. Naphthalene concentrations sampled are within the range of concentrations in which metabolic biomarkers have previously been observed (Phelps et al., 2002). The presence of M N A indicates that anaerobic degradation of methyl naphthalene is taking place at the site. Previous sampling of concentrations of 1-methyl naphthalene along the plume axis (Anthony, 1998) suggested that degradation is not a significant source of mass loss for this contaminant, but since this method provides only a qualitative indication of degradation, low level degradation of 1-methyl naphthalene is plausible. 32 M N A has been detected previously at sites where 2-NA, TH-2-NA, and HH-2-NA were also present. Although, data from only a few sites is presently available for comparison, M N A is generally the third most abundant metabolite. The detection of M N A without 2-N A at this site is difficult to explain with what is currently known about these substances, but it may be due to the complex hydrogeology at the site. Varying ratios of the metabolites at other sites (Phelps, et al., 2002) suggest that these metabolites have differing sorptive properties. Therefore, tidal and seasonal flow reversals at the site may explain the lack of 2-NA in the two groundwater samples. Previously, these metabolites have been observed in low gradient environments without tidal forcing (Phelps et al., 2002, Gieg and Suflita, 2002). The available data indicates that it is very likely that TH-2-NA is present at the site, although synthesis of TH-2-NA to confirm a matching spectra and retention time was not performed. Because of the lack of 2-NA at the site, and the lack of confirmation of the presence of TH-2-NA, this data is inconclusive. 4.3 Offshore Soil Sampling 4.3.1 Organic Carbon Analysis Organic carbon (OC) contents range from 0.09 to 0.52 % in core C02-1 and from 0.11 to 0.14 % in core C02-2. These results can be related to ICj values using an empirically-derived correlation equation appropriate to non-polar organics such as naphthalene (Schwarzenbach and Westall, 1981). K<j values for core C02-1 calculated with this equation range from 0.91 to 4.3 ml/g. The average K<i of all samples from core C02-1 is 1.14 ml/g. This value corresponds to an average retardation of 7.7. This average does not include the OC content of sample S-l because the OC of S-l was significantly larger than all other values and was considered representative of small scale, high organic carbon content regions present in the aquifer. K d values for C02-2 range from 0.93 to 1.17 ml/g and average 1.0 ml/g. This corresponds to an average retardation of 6.8. Complete data on organic carbon contents and K<j values is available in Table 4.3.1. Organic carbon contents analyzed by Anthony (1998) in cores collected onshore had an average K<j of 1.17. The agreement between organic carbon contents analyzed in cores 33 collected onshore (Anthony, 1998) and offshore (this research) implies that mass loss in the region of the plume that is beneath the river is likely not due to increased sorption and that the sediments at this site are relatively homogeneous. 4.3.2 Sorbed Naphthalene Direct extraction of sorbed naphthalene from core C02-1 was performed by soxhlet extraction (Bouchard 2003). Extractions were performed on each of the intervals analyzed for organic carbon from this core. The average sorption obtained from these extractions was 8785 pg/kg. Aqueous concentrations of naphthalene sampled in point R02-2 were used to compare sorbed concentrations with aqueous concentrations. Because of the horizontal extent of the plume and the relatively small horizontal displacement between C02-1 and R02-2, aqueous concentrations sampled at location R02-2 were considered to be representative of concentrations in C02-1. Naphthalene concentrations varied from 7 to 1237 ppb over the depth interval covered by the core. No relationship between aqueous concentration and sorbed concentration was observed. This result suggests that sorption to aquifer sediments is not at equilibrium with the aqueous phase. Desorption from the aquifer sediments must therefore be very slow and a K<j relation which assumes equilibrium sorption is not valid. In this case, sorption sites may now be saturated, and there is a possibility that the ability for further sorption is low. Assuming desorption from aquifer sediments is very slow, the amount of naphthalene currently sorbed could possibly represent the equilibrium sorption that would be reached before the plume began to recede due to containment of the source. Assuming an average aqueous concentration of 2000 ppb before the initiation of pumping, a K<i of 5.8 would be predicted. This value corresponds to an average retardation of 35. Previous sorption experiments performed by Anthony (1998) have yielded sorption much lower than that predicted by soxhlet extraction. Sorption isotherms performed on onshore sediments yielded non-linear retardation which was fit with a Freundlich relationship. This relationship describes equilibrium sorption using the following 34 equation */="Jr (Eq. 4.3.2.1) where S is the sorbed concentration, C is the aqueous concentration and b is a constant that describes the degree of non-linearity. Anthony (1998) fit sorption isotherm data with a b of between .728 and .869 which predicts higher retardation at low concentrations of naphthalene than at higher concentrations. Over the range of concentrations found in core C02-1, sorption isotherm data predicts retardations between 3.7 and 13.2. Because of the inconsistency of these results with other sorption data at the site and with what would normally be expected in this type of sediments, it seems likely that the results of soxhlet extractions may have been corrupted by analytical and experimental error. One possible source of error could be contamination of sediments from inadequate drying of samples before extraction. In addition, problems with the calibration of the GC for 1-fluoronaphthalene, which was used as the internal control to assess recovery, could also have contributed to error. Because of these concerns over the validity of results due to analytical and experimental problems, these extractions are currently being rerun with appropriate modifications to the experimental procedure and sample analysis. 35 5.0 Modelling 5.1 Groundwater Flow Model 5.1.1 Introduction A groundwater flow model was constructed to obtain a better understanding of the hydrogeology of the site and of the effects of seasonal changes in river stage elevation on the fate and transport of the contaminant plume. M O D F L O W (McDonald and Harbaugh, 1985) was used to simulate the hydrogeological conditions at the site. M O D P A T H (Pollock, 1989) was used to determine the path of a conservative tracer in the aquifer. The model was constructed using average monthly water levels and aquifer gradients to simulate seasonal variations in river stage elevations and recharge to the aquifer. The model represents the time period from August 1st, 1997 to July 31st, 2004. This period of simulation which extends beyond the time period for which data is available was used to allow for sufficient time to elapse for particle tracking results to be used to estimate residence times in the aquifer. The daily tidal variations in river stage were not explicitly simulated over the model's six-year time horizon. 5.1.2 Model Domain and Grid The domain of the model is 800 metres east-west by 780 metres north-south. The grid is most refined in the regions of the two source containment wells and at the tracer injection location (Figure 5.1.2.1). Based on the conceptual model (Golder, 1997); the aquifer was represented by several model layers with a cumulative thickness of 27 metres. Flat layer horizons were used, since the topographic variations at the site are generally less than 2 metres. Eleven model layers were used to resolve the vertically upward flow as groundwater discharges to the river. 5.1.3 Boundary and Initial Conditions Boundary conditions in the model (Figure 5.1.3.1) were derived from continuous water level monitoring data collected at the site (Golder, 1999). The locations of continuous water level monitoring wells are included in Figure 5.1.2.1. Continuous water level 36 monitoring data for two periods, spanning from April 1997 to December 1998 and from January to June 1999 was used. The gradients used in the model were derived from the range of values measured and adjusted during calibration. Table 5.1.3.1 displays the gradients input into the model and the range of gradients measured during continuous water level monitoring. Bathymetric data collected in the south-eastern portion of the model domain was used to delineate the bottom of the river boundary (Bianchin, 2001). A n average of seven surveys of bathymetric data collected between September 1998 and August 1999 was used. The northern and southern boundaries of the model were represented with time varying specified head boundaries. The eastern and western boundaries of the model were, for the most part, represented with no flow boundaries since the dominant direction of flow in the aquifer is north-south. The lower boundary of the aquifer was represented with a no flow boundary since the Pre-Fraser River sands unit which underlies the aquifer is considered to be of very low permeability (Golder, 1997). Because flow develops an east-west component beneath the river in response to the downstream river gradient, the constant head boundaries representing the river at the southern edge of the model were wrapped around the east and west edges of the model for approximately 50 metres beyond the natural bounds of the river. Beneath the specified head boundary representing the river at the southern edge of the model, a no flow boundary was used as suggested by the migration of the contaminant plume. The east-west river gradient assigned along the river boundary is 1.5xl0"4. This value was derived during calibration of the model to movement of the offshore bromide tracer. This method of derivation of the average river gradient was considered to provide the most reliable estimation of the average gradient as this data is both local to the site and averaged over 230 days. Other data that can be used to estimate this gradient are the river slope suggested by water level records collected at upriver and downriver hydrostratigraphic stations and by the gradient suggested by continuous water level 37 monitoring data. The Port Mann and New Westminster hydrostratigraphic stations are situated at approximately equal distances up and down river from the site. Data collected at these hydrostratigraphic stations between May 25 t h, 2002 and May 25 t h, 2003 was used to estimate an annually averaged river gradient of 1.75xl0"5. Average monthly river gradients may also be estimated from continuous water level monitoring data taken from wells DT-5 and DT-15, which are approximately 130 metres apart and are located 15 and 10 metres from the shoreline, respectively. River gradients calculated from well data from December 1998 to October 1999, range between 1.7xl0"4 and 4xl0" 3. Although the effect of the cone of depression from the two pumping wells at the site may cause data from continuous water level monitoring to overestimate the river gradient, the greatest river gradients recorded in these wells coincide with periods when the influence of the pumping wells is expected to be at a minimum. This suggests that the gradient calculated from continuous water level monitoring data is more strongly influenced by the river gradient than by pumping. A sensitivity analysis was performed to assess the effects of river gradient on model predictions. Results of this analysis are included section 5.1.9. This assessment was performed because of the large variance in estimates of the river gradient. A sensitivity analysis of hydraulic conductivity was not performed, as through pumping test data, this parameter was considered to be better constrained than gradients. A sensitivity analysis of recharge was not performed, as during calibration, this parameter was not found to significantly alter model results with a reasonable range of model input. Recharge to the model was estimated as a percentage of average monthly precipitation. A previous site water balance suggested that a greater percentage of precipitation infiltrates from April to September of each year than during the fall and winter (Golder, 1997); therefore, recharge in the model was set to a greater percentage of precipitation from April to September than from October to March. Although a greater percentage of precipitation infiltrates April to September, total recharge to the aquifer is greater from 38 October to March. Table 5.1.3.2 displays monthly recharge rates input into the model. The initial condition used for simulations was the distribution of heads obtained from a steady state simulation under average flow conditions. To minimize the impact of this initial condition, particle tracking results from the first year simulated were not analyzed. 5.1.4 Parameter Values Because of the unavailability of spatially distributed continuous water level monitoring data and the small area of transport covered by the tracer plume, a single averaged value of transmissivity and storage were used to represent the majority of the model domain. The transmissivity and storage values used in the model were derived from pumping tests performed at source containment wells (Golder, 1997). A second conductivity zone directly underneath the river was added to reproduce the direction of flow indicated by plume movement (Figure 5.1.4.1). The aquifer was assigned a conductivity of 5xlOA m/s and a specific storage of 2xl0" 4 1/m. Consistent with previous work, the aquifer was assigned a porosity of 0.25 (Anthony, 1998). This conductivity zone which represents the silty sediments encountered during profiling in this work and in previous sampling rounds (Anthony, 1998, Lesser, 2000) was assigned a conductivity of 4xl0" 5 m/s. 5.1.5 Source Containment Wells To contain the D N A P L source, pumping well DWW-3 was installed in the aquifer in 1996. This well was used for source containment until groundwater modelling performed by Golder (1999) demonstrated that better capture of the source zone could be achieved with a well positioned approximately 70 metres to the east of DWW-3. Well DWW-5, replaced well DWW-3 in July of 1999. Accurate average monthly pumping rates for both wells used to capture the plume source were input into the model for the time period from August 1997 to July 2002. Because pumping rates beyond August 2002 were not available, monthly pumping rates from August 2001 to July 2002 were input into the model to represent the time period from August 2002 to July 2004 as well. This approximation does not affect the calibration of the model as the tracer plume used for calibration of the model was not monitored beyond the year 2000. Because this model assumes that pumping rates beyond July 2002 will remain stable, i f pumping rates are 39 dramatically increased or decreased, estimates of residence times in the aquifer wil l be affected. 5.1.6 Calibration The model was calibrated by correlating particle tracking results with the transport of the bromide tracer released in February 2000 (Bianchin, 2001). This bromide tracer plume was monitored offshore for 230 days after release. Care was also taken to ensure that particle tracking results were consistent with groundwater flowpaths indicated by distribution of the groundwater plume during initial profiling in 1996. These criteria were chosen because, unlike instantaneous water-level measurements, the cumulative transport and distribution represents average hydraulic gradients and, therefore, the effects of tidal fluctuations would be averaged out. Because the tracer plume was observed to move over a very small distance during the course of sampling for 230 days, movement of the plume does not provide information on parameter values over a very large region of the aquifer. In addition, after the first 48 days that the plume was monitored it no longer had a well defined centre to correlate with particle tracking results. This non-uniform spreading of the plume is likely due to heterogeneity in the flow field, sampling limitations, and tidal mixing which are not taken into account in this groundwater model. Details of the calibration and a sensitivity analysis are included in Appendix G. 5.1.7 Seasonal Variations in Aquifer Gradients Groundwater modelling shows that flow in the aquifer oscillates on a seasonal time scale, due to changing river stage elevations and fluctuations in pumping rates. As shown by Zawadzki et al. (2002), changes in river stage and pumping throughout the year cause the influence of the source containment well on the contaminant plume to be highly seasonally dependent. During periods of high river stage elevation, the well influence extends to the region of the aquifer beneath the Fraser River and causes migration of contaminants to slow or become directed away from the river. Figure 5.1.6.1 compares groundwater flow directions along the plume axis in June with 40 groundwater flow directions in February. The relative sizes of arrows in this figure reflect the magnitudes of groundwater velocities over the cross section. In February, flows in the region of the aquifer beneath the river are directed towards the river and velocities are much greater than in June. In June, groundwater velocities beneath the river are directed away from the river. Particle tracking shows that particle movement is directed downwards and away from the river during periods of high river stage. During the freshet, particles migrate up to 4 metres away from the discharge point in the offshore region of the plume. 5 . 1 . 8 R e s i d e n c e t i m e s Although the source containment well at the site does not capture the entire aqueous phase plume throughout the year, seasonal fluctuations in the well influence extend the residence time of contaminants that eventually discharge to the river. This increase in residence times increases the opportunity for attenuation of contaminants. Particle tracking results can be used to illustrate the increase in residence times associated with the pumping well. Figure 5.1.7.1 demonstrates the change in the flowpath of offshore waters due to the influence of the pumping well. For a particle beginning at location R96-1 released in October when sampling in 1996 took place, the residence time of the particle in the aquifer increases from 400 to 1400 days due to the influence of pumping. These particle tracking results predict that the bromide tracer injected in the year 2000 would have a residence time of 1000 days. Between the time of injection and sampling in June 2002, the centre of mass of the bromide tracer is expected to have travelled approximately 35 to 40 metres beyond the injection point. This position is outside of the area sampled in June 2002, and therefore this result is consistent with low bromide concentrations sampled in recent profiling. 5 . 1 . 9 I m p l i c a t i o n s f o r P l u m e S h a p e Particle tracking results show that although the transport of contaminants offshore is 41 influenced by the pumping well at the site, the capture zone of the well is presently restricted to the onshore region of the plume. Figure 5.1.7.1 illustrates particle tracking results for particles released in June when aquifer gradients are low and the capture zone of the well near its maximum. This result is consistent with transport of the offshore bromide tracer which was used for calibration criteria. These results provide further evidence that attenuation of naphthalene is responsible for the rapid decline in concentrations in the offshore region of the plume. Because contaminants are slowly moving towards the river, to explain low concentrations observed offshore, mass loss must occur. The sharper decline in concentrations in the offshore region of the plume sampled in 2002 and 2003 may be explained by the increased residence times of particles in the aquifer. Because particles are moving more slowly, i f degradation occurs at same rate as it did prior to pumping, mass loss along the flowpath of the plume wil l become more pronounced and the plume front will sharpen. Particle tracking results also show that the east-west component of flow is significant in the aquifer. In the offshore region of the plume, the influence of the river gradient causes particles to discharge west of their release point. Particles are observed to discharge further west under the influence of pumping in the aquifer due to increased residences in the aquifer. In the absence of the pumping well at the site, a particle beginning at profiling location R96-1 is observed to become displaced 11 metres west before reaching its discharge point. In the presence of the pumping well, a particle released at R96-1 will discharge 26 metres west of its release point. This result suggests that the offshore plume discharges west of the onshore plume profile. Particles released onshore to the east of the source zone, but outside of the capture zone of the source containment well are displaced westward by the influence of the well before reaching the offshore region. These results suggest that although the concept of the flowpath of the plume as perpendicular to the river flow was a reasonable assumption prior to the initiation of pumping, current directions of groundwater flow are more 42 complex. 5.1.10 Sensitivity Analysis Because of the uncertainty in gradients along the river boundary and between the northern boundary and the river, an analysis of the sensitivity of model predictions to variations in these gradients was performed. Simulations were run in which each of these parameters were individually adjusted to what were considered reasonable upper and lower bounds. The minimum bound for the river gradient was set to 2x10~5. This gradient was estimated from data collected from hydrographic stations located up and down gradient from the site between 2002 and 2003. Results of this simulation are displayed in Figure 5.1.9.1. This figure shows that when the river gradient is low, the capture zone of the well is greater than in the calibrated model on the western side of the well, but still restricted to the onshore zone of the plume. In this simulation, the residence time of a particle released at point R96-1 increases to 1600 days from 1400 days in the calibrated simulation. In addition, a particle released at R96-1 discharges to the east of the release point rather than to the west. The maximum bound for the river gradient was set to 3xl0" 4. This gradient is 2.1 times the value used in the calibrated simulation. The river gradient predicted by continuous water level monitoring (CWLM) data was not used as the maximum bound as this data was considered to overestimate the river gradient due to the effect of the cone of depression of the capture wells at the site and the small distance of separation between the two C W L M wells along the shoreline. Results of the high river gradient simulation are displayed in Figure 5.1.9.2. This figure shows that when the river gradient is low, the capture zone of the well is smaller on the western side of the well, and is still restricted to the onshore zone of the plume. In this simulation, the residence time of a particle released at point R96-1 decreases to 900 days from 1400 days in the calibrated simulation. In addition, a particle released at R96-1 discharges 40 metres to the west of the release point rather than 26 metres. 43 To estimate the maximum and minimum bounds for the gradient between the northern boundary of the model and the river boundary, the maximum and minimum monthly north-south gradients observed over the period of C W L M were used. In the simulation in which the maximum monthly gradients were used, the extent of capture zone of the well is significantly diminished from the calibrated scenario (Figure 5.1.9.3). Particles located over 20 metres north of the shoreline discharge to the river in the region of the maximum southern extent of the well influence. In this simulation, the residence time of a particle released at point R96-1 decreases to 500 days from 1400 days in the calibrated simulation. In addition, a particle released at R96-1 discharges 13 metres to the west of the release point rather than 26 metres. In the simulation in which the minimum monthly gradients were used, the capture zone of the well extends over 70 metres south of the shoreline (Figure 5.1.9.3). In this simulation, a particle released at point R96-1 is captured by the source containment well. The results of these simulations show that predictions of the calibrated groundwater flow model are not very sensitive to the uncertainty in the river gradient. Although flowpaths of contaminants in the aquifer are affected by changes in this parameter, the effect on the influence of the source containment well at the site and the residence times of contaminants in the aquifer is moderate. Simulations to examine the sensitivity of model predictions to changes in North-South aquifer gradients show that annual variation in monthly aquifer gradients has a significant impact on travel times in the aquifer and the capture zone of the source containment well at the site. These results suggest that the annually averaged capture zone may vary significantly from year to year due to annual variations in the north-south gradient. A summary of results of sensitivity analyses is included in Table 5.1.9.1. 5.2 Geochemical Model 5.2.1 Model Objectives A batch model was prepared to examine the effects of iron reduction and methanogenesis on geochemistry at the site and to estimate the bounds of concentration reduction that could be explained by degradation. Although, this model neglects flow and therefore changes in water chemistry due to tidal forcing, dispersion, and contaminant migration, 44 the effects on water chemistry that could be expected due to geochemical processes may be examined. Phreeqc 2.7.1 (Parkhurst and Appelo, 1999) was the code used to construct the batch model. 5.2.2 Batch model design The batch model was designed to understand changes in water chemistry that could be expected for a packet of water beginning at sampling point R96-1 along its flowpath. The composition of the initial solution was determined from data collected in 1996 (Anthony, 1998) to represent the initial state of the plume core. Initial chemistry of the solution used in the batch reaction was obtained from data observed in offshore sampling point R96-1 (Anthony, 1998). Because pH was not recorded in sampling point R96-1, the initial pH used in the batch model had to be estimated from alternate sources. A n initial pH of 6.2 was used as the upland groundwater has been reported to be 6.2+A.2 (Anthony, 1998). This value was considered reasonable as pH values within the plume recorded in 1999 were reported to be between 5.6 and 7.2 (Bianchin, 2001). The alkalinity reported for sampling point R96-1 was not used in the batch model as this value is an order of magnitude lower than all other alkalinities reported in the plume. Instead, the alkalinity of the initial solution was estimated from alkalinity data obtained during sampling in 2002 and 2003. Composition of the initial solution is displayed in Table 5.2.2. Based on the results of soxhlet extractions (Bouchard, 2003) which suggest that desorption in the aquifer is very slow and further sorption is low, naphthalene was considered to be non-sorptive and the effects of buffering of aqueous naphthalene concentrations by desorption were considered negligible. Based on particle tracking results from the groundwater flow model, the batch model was run for 600 days to represent the residence time of a particle in the aquifer released at point R96-1 before the initiation of pumping and for 1400 days to represent the residence time of a particle after the initiation of pumping. Degradation of naphthalene by iron reduction and methanogenesis was represented in the 45 batch model by irreversible kinetically controlled reactions with a Monod type rate expression (Bekins et al., 1998). The equations used to describe these reactions are as follows (Bianchin, 2001). 48Fe(OH)3 + C , 0 H 8 => 10CO 3 2" + 48Fe 2 + + 38H 2 0 + 760H" (Eq. 5.2.2.1) CioHg + 12H 2 0 => 6 C H 4 + 4C0 3 2 " + 8 H + (Eq. 5.2.2.2) Rates used in the model were estimated from laboratory microcosm experiments (Lesser, 2000) and a radiolabeled naphthalene tracer experiment (Bianchin, 2001). Lab microcosms performed on soil and water collected from within the aquifer and spiked 13 1 1 with naphthalene produced an average degradation rate of 4.7 x 10" mol-1" -s" (1900 pg-f'-yr"1) (Lesser, 2000). Bianchin (2001) reported a zero order 1 4 C - C 0 2 production rate of 6.7 x 10"17 mol-1"1-s"1. Correcting this production rate for a dilution factor of 5.3 (Bianchin, 2001), and using the ratio of the radiolabeled naphthalene tracer to naphthalene concentrations in the contaminant plume at the injection location, a zero-order estimate of naphthalene degradation can be determined. The range of degradation rates determined from this analysis is 5.15 x 10"14 to 5.15 x 10"13 mol-f'-s"1 (208 to 2008 pg-f'-yr"1). These values were used to constrain the degradation rates used in the model. To the knowledge of the author, no published data on naphthalene half saturation constants under iron-reducing or methanogenic conditions is available although half saturation constants between 0.09 and 3.4 mg/1 have been found for naphthalene under aerobic conditions (Knightes and Peters, 2000, Ghosdal and Luthy, 1998, Guerin and Boyd, 1992). Because no data on half saturation constants for this site was available, a half saturation constant of lx l0" 6 M (0.128 mg/1) was determined by calibrating to field data. Figure 5.2.2.1 displays a plot of the fit of modelled naphthalene concentrations to field sampled concentrations along the flowpath using the best fit half saturation constant of lxlO" 6 M and the maximum level of degradation determined by Bianchin (2001). Figure 5.2.2.2 displays a plot of the total error between field and modelled naphthalene concentrations 46 for half saturation constants between 5x10~7 and lxlO" 5 . For this analysis, the time of transport along the flowpath to field sampling points was estimated from results of the groundwater flow model. A complete listing of input and output of the batch model is available in Appendix H and Appendix I. 5.2.3 Degradation of Naphthalene by Iron reduction and Methanogenesis Results of batch modelling show that prior to pumping in the aquifer a reduction in naphthalene levels between 220 and 2150 pg/1 along the flowpath of the plume can be explained solely by degradation. As some decrease in naphthalene concentrations may be attributed to the effects of tidal forcing and dispersion, this range of degradation is consistent with naphthalene levels observed along the flowpath of the plume in 1996. In 1996, naphthalene concentrations were observed to decrease from 3797 pg/1 to 64 pg/1 from sampling point R96-1 to R96-7 located at the discharge point of the plume. Naphthalene concentrations observed in 1996 may also show greater mass loss than the model due to the initiation of source containment approximately three months prior to sampling. When rates of degradation of naphthalene by iron reduction and methanogenesis are assumed to be equal, levels of dissolved iron in the model increase to between 51 and 72 mg/1 in the simulation in the absence of pumping. These results are consistent with iron levels of up to 63 mg/1 sampled along the flowpath of the plume in 1996; however other processes such as mineral dissolution or precipitation, surface complexation, and degradation of organic matter may also affect ferrous iron concentrations. Because these other processes may be taking place, this result demonstrates that the rate of degradation by iron reduction used in this simulation is a possible scenario, but cannot conclusively demonstrate that this is the rate of iron reduction taking place at the site. Dissolved methane levels increase to between 6.1 and 6.8 mg/1 over the course of the simulation. These methane levels are much lower than those sampled along the flowpath of the plume in 1996 which were up to 21.4 mg/1. 47 Under the influence of pumping, the minimum bound of degradation (Bianchin, 2001) predicts that 763 p.g/1 of naphthalene would be degraded along the flowpath. The maximum bound of degradation predicts that all of the naphthalene initially present would be degraded in 760 days. Relating these results to groundwater modelling, this would represent complete degradation approximately 12.3 metres along the flowpath from sampling point R96-1. During sampling in 2002, concentrations decreased from over 2000 pg/1 to less than 8 p.g/1 over 6 metres in the zone of mass loss. During sampling in 2003, concentrations decreased from over 1300 to llp.g/1 over 7 metres in this zone. These results imply that the maximum rate of degradation provides a better fit to field data. Levels of dissolved iron in the model increase along the flowpath to between 57.1 and 88.7 mg/1 in this simulation. Iron levels up to 76 mg/1 were sampled along the flowpath of the plume in 2002 and 2003, but were not observed to increase along the flowpath. Dissolved methane levels increase to between 6.3 and 7.4 mg/1 over the course of the simulation. Methane levels sampled in 2002 and 2003 were up to 13 mg/1 along the flowpath of the plume. These higher methane levels sampled in the field may be due to degradation of organic matter by methanogenesis not taken into account in this simulation. The batch model cannot be calibrated using observed naphthalene degradation because it neglects the effects of tidal forcing and dispersion. However, the above results suggest that the degradation rate predicted by lab microcosms and the maximum level of degradation predicted by the radiolabeled tracer best fit the observed data. For this reason, further simulations utilize the maximum level of degradation predicted by the tracer experiment. In addition, because more complete geochemical data is available for the aquifer under the influence of the source containment well at the site further simulations utilize the residence time of contaminants under the influence of this well. 5.2.4 Influence of Degradation on pH and Alkalinity Degradation of naphthalene by iron reduction was found to increase pH. When rates of degradation by iron reduction and degradation by methanogenesis are equal, pH increases 48 to 6.6. pH values within the plume observed in 1999, three years after the initiation of source containment (Bianchin, 2001), were generally below 7. During sampling in 2002 and 2003, pH was observed to increase to 6.7 over the flowpath of the plume; therefore pH predicted by initial modelling where degradation of naphthalene takes place by a combination of iron reduction and methanogenesis is consistent with field data. Alkalinity was observed to increase to 5.5 meq/1 when rates of degradation by iron reduction and degradation by methanogenesis are equal; this is also consistent with field data observed during sampling for this study. 5.2.5 Degradation of Organic Matter As discussed in the preceding chapter, degradation of organic matter by iron reduction may also be occurring in the aquifer. Degradation of organic matter by iron reduction follows the equation C H 2 0 + 4Fe(OH)3 + 6 H + ^ C 0 3 2 " + 4Fe 2 + + 10H 2O (Eq. 5.2.8.1) This process wil l produce increased pH and ferrous iron in the aquifer. Field sampling in 2002 and 2003 resulted in pHs that gradually increase to 6.7 over the flowpath. This increase in pH continues to occur beyond the region of mass loss of naphthalene suggesting that degradation of organic matter by iron reduction occurs in this zone. High iron concentrations sampled in shallow sampling intervals, outside of the plume flowpath confirm degradation of organic matter by iron reduction. Lower methane levels were detected in an uncontaminated sampling point downgradient from the plume than in the plume itself. In addition, methane levels increase along the plume flowpath in the region sampled in 2002 and 2003. These data suggest that processes specific to the plume create favourable conditions for degradation by methanogenesis. Because of the discrepancy between sampled and simulated levels of methane, the possibility that processes within the plume may cause organic matter to degrade by methanogenesis was examined. Degradation of organic matter by methanogenesis by the equation 49 2 C H 2 0 + H 2 0 => C H 4 + H + + H C 0 3 " (Eq. 5.2.8.2) will produce methane and decrease pH. To investigate the effect of degradation of organic matter by methanogenesis on the pH in the aquifer, simulations were performed which incorporate degradation of organic matter. Rates of naphthalene and organic carbon degradation may be interrelated (Mihelcic and Luthy, 1988) and vary spatially. Due to the complexity of attempting to model this process combined with the lack of information on degradation rates and dissolved organic carbon, this modelling provides only a starting point for understanding the effects of degradation of organic matter on geochemistry. Degradation of organic matter was represented in the model as a kinetic zero order reaction. Using this method, the amount of organic carbon in the solution did not need to be specified; instead, the rate of degradation of organic carbon by methanogenesis was input into the model. Because dissolved methane levels collected in February 2003 were considered more reliable than methane levels collected in June 2002, February 2003 methane data were used as a calibration target for methane levels along the flowpath in these simulations. In February 2003, dissolved methane levels up to 13 mg/1 were observed along the flowpath. When dissolved methane levels reach 12.6 mg/1 along the flowpath, organic matter degrades by methanogenesis at a rate of 3.0 x 10"12 mol/l-s. In this simulation, pH increases to a maximum of 6.55 at which point all the naphthalene is exhausted. After all the naphthalene in the simulation has degraded, the pH then begins to decrease slightly to 6.53. In the simulation without degradation of organic matter, the pH of the system reached 6.6 over the flowpath. Because degradation of organic matter decreases pH by only 0.07, this effect is likely too small to be observed in the field. 5.2.6 Degradation solely by iron reduction Because degradation of naphthalene by iron reduction is better documented than 50 degradation of naphthalene by methanogenesis, the possibility that all degradation of naphthalene at the site is due to iron reduction was investigated. In this simulation, all methane produced is due to degradation of organic matter. Because all degradation of naphthalene in this simulation occurs by iron reduction, this degradation rate was set to the upward bound of naphthalene degradation determined from Bianchin (2001). Results of batch modelling show that iron concentrations increase to 128.5 mg/1 when iron reduction is the sole mode of degradation of naphthalene. pH increases to between 7.0 and 7.1 over the course of the simulation. These iron and pH levels are higher than those observed at the site. Because levels of ferrous iron produced during the simulation where degradation of naphthalene occurs solely by iron reduction were much greater than those observed in the field, the possibility that iron consuming processes such as precipitation of iron minerals and surface complexation of iron may be taking place was considered. Simulations which incorporate each of these processes were performed and are discussed in the following two sections. 5.2.7 Mineral precipitation The saturation indices of pyrite (FeS2) and siderite(d) (FeCOs) were observed to increase to above saturation over the course of simulations. The precipitation of these minerals will consume iron in the aquifer. Precipitation of siderite will also decrease pH by consuming carbonate. A simulation was run in which all degradation in the aquifer occurs by iron reduction and the water in the aquifer is in equilibrium with both of these minerals. In this simulation, pyrite and siderite precipitate by the following equations. Fe 2 + + 2HS" <=> FeS 2 + 2H + + 2e" log k = 18.479 (Eq. 5.2.7.1) Fe 2 + + C 0 3 2 " <=> FeC0 3 log k = 10.45 (Eq.5.2.7.2) Equilibrium constants used were taken from the Wateq4f database (Ball and Nordstrom, 51 1991). When pyrite and siderite are in equilibrium with the water in the aquifer, iron levels decrease to 13.6 mg/1 along the flowpath and pH decreases to a maximum of 6.4 over the course of the simulation. These levels of ferrous iron and pH are much lower than observed in field data. If only siderite precipitation takes place, a minimal change in results is observed. This simulation shows that although mineral precipitation may reduce iron and pH levels in the aquifer, water in the aquifer is not in equilibrium with either of these two minerals. Instead, i f mineral precipitation is taking place, the rate of precipitation is limited. Rate limited precipitation may produce similar iron and pH levels to those observed in the field. 5.2.8 Surface Complexation of Iron Because of the high iron levels in the aquifer, surface complexation of iron to hydrous ferric oxides may buffer higher iron concentrations produced during iron reduction. Surface complexation of iron will also displace protons at surface sites into the aqueous phase thereby reducing pH. Simulations were performed to understand the effect this mechanism would have on the geochemistry of the system. Because site specific data was not available, equilibrium constants used in this modelling were taken from Dzombak and Morel (1990). These constants are highly site specific; therefore results of these simulations provide only a starting point for understanding the effect of surface complexation on geochemistry. Surface complexation of iron to hydrous ferric oxides follows the equations: H f o O H + Fe 2 + <=> H f o OFe + + H + log k = -2.98 (Eq. 5.2.7.1) HfoOH + Fe 2 + +H 2 0 <^> H f o OFeOH + 2 H + log k = -11.55 (Eq. 5.2.7.2) 52 These are pH dependent processes with greater sorption at lower pH values. Changes in log k values will greatly change the influence of these processes at a given pH. Sorption sites for hydrous ferric oxides are divided into strong and weak sites (Dzombak and Morel, 1990). The number of weak sites corresponds to the total amount of sorption sites while the number of strong sites corresponds to the amount of high affinity cation binding sites. Implementing weak surface complexation in the batch model where all degradation of naphthalene takes place by iron reduction, iron is limited to 79.6 mg/1 and pH increases to 6.7 over the course of the simulation. These values are consistent with data observed in the field. Adding strong sorption sites to this simulation has a negligible effect on results. 5.2.9 Discussion of Limitations Although this model provides insight into geochemical processes taking place in the aquifer, because it neglects flow and because of uncertainties in parameters, direct application of this model to conditions observed in the field is limited. Processes of dispersion and tidal forcing not taken into account in this model wil l dilute contaminant concentrations and increase mixing of nutrients. Sorption wil l increase residence times in the aquifer, and therefore, the opportunity for degradation of naphthalene. Interactions between rates of organic carbon and naphthalene degradation may also be present. The assumption that sorption sites in the aquifer are saturated is based on results of soxhlet extractions. Sorption isotherm experiments on offshore contaminated sediment are necessary to confirm this assumption. If sorption sites are not saturated and retardation of naphthalene is greater than 1, slower degradation rates would be used in the model to fit the geochemical data. The batch model functions based on the assumption that solid phase geochemistry is constant along the flowpath. This assumption neglects the possibility of different geochemical zones with varying ferric oxide and organic carbon contents along the flowpath. Because of the expected homogeneity in the aquifer matrix, this assumption is 53 not expected to significantly change results, except in the region of the aquifer very near the river/aquifer interface where the composition of the aquifer may change significantly. A summary of results of batch modelling is included in Table 5.2.9.1. 54 6.0 Conclusions and Recommendations The effects of biodegradation, mass stored in the aquifer matrix due to sorption, complex geochemistry and dynamic site hydrogeology must all be accounted for in order to explain the contaminant fate and transport of the creosote-derived plume at this site. In this study, the results of field sampling, groundwater flow modelling, and geochemical modelling were employed to understand processes contributing to spatial and temporal changes in plume composition and geochemistry. 6.1 Groundwater flow The results of groundwater flow modelling show that flow in the aquifer is complicated due to the influence of the capture well at the site and seasonally varying aquifer gradients. Due to movement of the well influence with the spring freshet, contaminants at the fringes of the capture zone are transported towards the river at times of low river stage and away from the river at high stage. Field sampling of aqueous naphthalene concentrations during high and low gradient periods shows this seasonal fluctuation in gradients results in minimal seasonal displacement of naphthalene. Particle tracking results show that although offshore contaminants are slowed by the influence of the well, the capture zone of the well is restricted to the onshore region of the aquifer. This variance in the capture zone extends the residence times of contaminants in the aquifer, increasing the opportunity for attenuation of contaminants before discharge to the river. 6.2 Contaminant Plume Continued high naphthalene concentrations sampled in 1999 despite source containment for three years led to the hypothesis that the plume may be at steady state due to buffering of contaminant concentrations by desorption from aquifer sediments. Naphthalene concentrations sampled in this round show that the contaminant plume is not at steady state. Particle tracking results and sorption data show that the continued presence of high concentrations of naphthalene offshore are likely due incomplete source containment or to slow migration of contaminants from upgradient regions of the aqueous plume. Reduced contaminant concentrations sampled in this round suggest mass loss by biodegradation. Although tidally driven mass loss is expected to contribute to decreased 55 concentrations in the portion of the aquifer underneath the river (Yim and Mohsen, 1992), assuming a constant flux from the source zone over the time scale of transport, relative enrichment of benzothiophene and indane along the plume profile despite these compounds lower sorptive properties and therefore greater susceptibility to tidally-driven mass loss proves that observed loss of naphthalene over the plume flowpath is not due to a physical process. In addition, geochemical modelling confirms that the observed reduction in concentrations between this sampling round and previous sampling is within, the range predicted by lab microcosm and field tracer study derived degradation rates (Lesser, 2000, Bianchin, 2001). Although naphthalene has been the focus of all previous investigations of the offshore plume at this site, recent sampling shows that indane and benzothiophene become the dominant components of the aqueous phase plume towards the discharge point. Although the impact of these two contaminants on aquatic life has yet to be determined, their toxicity is a possible focus for further research both at this site and potentially at other sites of historic creosote contamination. 6.3 Geochemistry High concentrations of iron and dissolved methane are present throughout the plume axis, but not in background data collected outside of the plume at a comparable distance offshore. This data suggests that high iron and methane concentrations along the plume flowpath are associated with iron reducing and methanogenic processes specific to the contaminated area. Acetate levels in the plume suggest methanogenesis and limited iron reduction although no appreciable difference in acetate levels is present between background data and the majority of data in the plume. Concentrations of dissolved methane increase along the plume flowpath, but iron concentrations do not. Geochemical modelling shows that this lack of increase in iron may be due to surface complexation or mineral precipitation. High iron concentrations near the discharge point previously attributed to degradation of naphthalene along the flowpath are likely due to increased degradation of organic matter due to iron reduction near the river bottom. 56 Geochemical modelling shows that degradation of naphthalene may be taking place by a combination of iron reduction and methanogenesis or by iron reduction alone. Results of simulations show that degradation of naphthalene by methanogenesis alone cannot explain the methane levels observed in the aquifer. Further modelling shows that dissolved methane levels sampled in the field may be higher than initial modelled values due to degradation of organic matter. If naphthalene degradation takes place solely by iron reduction, high pH and iron result. Surface complexation of iron or precipitation of iron minerals may buffer this higher pH and iron to levels consistent with field data. 6.4 Recommendations for Further Research Further soxhlet extractions to determine sorbed naphthalene on field aged sediments is recommended to confirm the results of Bouchard (2003) used in geochemical simulations. In addition, desorption experiments are recommended to determine the rate of desorption from offshore sediments. Sorption isotherms on offshore core would provide an idea of the capacity of offshore sediments for further sorption and confirm the assertion from organic carbon results that sorption is relatively homogeneous between the onshore and offshore regions. 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Evidence of aromatic ring reduction in the biodegradation pathway of carboxylated naphthalene by a sulphate reducing consortium. Biodegradation. 11: 117-124 63 Clayey Silty Overbank Deposits (3 - 5 metres) Gravel and Silt Fill ( 1 -2 metres) Fraser River Sands (20.5 to 30.5 metres) Pre-Fraser River Sands (silty-, sandy- and gravelly-interbeds) Figure 2.1.1 Hydrostratigraphy Fig. 2.3.1 Site Map 65 Distance (m) N- -»S Net g.w. flow direction Vertical Exaggeration = 2 9 5000+ ug/l 500 - 5000 ug/l 50 - 500 ug/l 5- 50 ug/l Fig. 2.3.2 Profiling Results 1996 (Modified from Anthony, 1998) 66 Ship 's Boom Tef lon Tubing A W R o d s Sampl ing Sys tem Profi ler Tip Figure 3.1.1 Profiling System 67 Figure 3.1.2 Sampling System N Naphthalene Contour 1996-1999* (ppb) f \ Inferred extent of Intermediate \ ) N A P L " \ s h o r e l i n e \ Cross section A-A' • Profiling Point 1996 • Profiling Point 2002 " Golder 1998 Meters ' Maximum Naphthalene Concentration Data from Anthony(1998), Bianchin(2001), Lesser(2000) Figure 3.2.1 Profiling Locations June 2002 6 9 -20 0 Distance (m) 40 60 Meters N ) S Net g.w. flow direction Vertical Exaggeration = 2 5000+ ug/l* 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* • Profiling Interval June 2002 * Naphthalene Contours 1996 (Anthony, 1998) Figure 3.2.2 Profiling Depth Intervals June 2002 The rectangular outline represents the region sampled in 2002. v Naphthalene Contour 1996-1999* (ppb) r\ Inferred extent of Intermediate U NAPL** \ s h o r e l i n e \ Cross section A-A' • Profiling Point 1996 • Profiling Point 2002 A Profiling Point 2003 " Golder 1998 20 40 Meters * Maximum Naphthalene Concentration Data from Anthony(1998), Bianchin(2001), Lesser(2000) Figure 3.3.1 Profiling Locations February 2003 71 N-0 3 6 Meters •+S Net g.w. flow direction Vertical Exaggeration = 2 5000+ ug/l* 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* • Profiling Interval February 2003 * Naphthalene Contours 1996 (Anthony, 1998) Figure 3.3.2 Profiling Depth Intervals February 2003 72 Outer E W Rod Inner R W Rod Aluminum Sampling Tube • Rubber O-rings • Drive Point Soil Coring Interval Soil Core Catcher 1 s t Outer E W Rod Aluminum Sampling Tube Soi l Core Sample Soi l Core Catcher Figure 3.4.1.1 Coring System 73 ->S Net g.w. flow direction Vertical Exaggeration = 2 O 5000+ ug/l* HH 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* I Soil Core interval [1 Radiolabeled Naphthalene Injection interval (Bianchin, 2001) * Naphthalene Contours 1996 (Anthony, 1998) Figure 3.4.2.1 Soil Core Interval 74 Naphthalene Contour 1996-1999* (ppb) r \ Inferred extent of Intermediate W N A P | _ « \ s h o r e l i n e \ Cross section A-A' • Profiling Point 1996-1999 • Profiling Point 2002 " Golder 1998 20 40 Meters * Contour of Maximum Naphthalene Concentration Data from Anthony(1998), Bianchin(2001), Lesser(2000) Figure 4.1.1.1 Maximum Naphthalene Concentrations June 2002 75 ->S Net g.w. flow direction Vertical Exaggeration = 2 5000+ ug/l 500 - 5000 ug/l 50 - 500 ug/l 5- 50 ug/l • Profiling Interval June 2002 The black outline in the top window represents the area magnified in the bottom window. Figure 4.1.1.2 Naphthalene Concentrations Top: 1996 Bottom: June 2002 76 N-• 64.9 • 109 • 41.7 • 112 • 47.9 * • 54.5 49.1 • 47.3 $48 • 51.5 • 75.8 • 70.7 • 26 • 24.8 •21 • • 36.9 43.4 • 41.2 0 3 6 Meters Profiling Interval June 2002 ->S Net g.w. flow direction Vertical Exaggeration = 2 • 5000+ ug/l* 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* * Naphthalene Contours June 2002 Figure 4.1.2.1 Iron Concentrations June 2002 (mg/l) 77 Meters • Profiling Interval June 2002 N >S Net g.w. flow direction Vertical Exaggeration = 2 4) 5000+ ug/l* 500 - 5000 ug/l* 50-500 ug/l* 5- 50 ug/l* * Naphthalene Contours June 2002 Figure 4.1.2.2 Nitrate Concentrations June 2002 (mg/l) '16.3 •29.5 •14.2 • 18.4 •11 •199.5 2 5 3 - 3 « 1 2 . 4 . 2 1 . 5 •12.1 •18.1 •17.1 •17.6 •19.9 •18.9 •39.6 •16.1 • 2 3 • 20.7 • 2 6 ? 1 . 4 « 19.4 • 7 . 6 • 47.3 • 27.4 • 21.3 • 16 • 20.6 • 5 7 ^10 .4 ° ' • ND 0 3 Meters N-Profiling Interval June 2002 ">S Net g.w. flow direction Vertical Exaggeration = 2 5000+ ug/l* 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* Naphthalene Contours June 2002 Figure 4.1.2.3 Acetate Concentrations June 2002 (uM) 79 •0.4 •2.3 • 4.7 *6.1 •2.4 •2.9 •7.9 •3.8 •1.5 •2.0 •0 .9 •10.7 *8.1 •7 .2 •5.1 •3 .0 • ND • 6 . 8 # N D # N D •8.0 '5.6 • •7 .6 9.5 9.6 5.4 • 6.3 9.2 '4.4 5.7 0 _ 3 6 Meters Profiling Interval June 2002 N- ->S Net g.w. flow direction Vertical Exaggeration = 2 5000+ ug/l* 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* Naphthalene Contours June 2002 Figure 4.1.3.1 Dissolved Methane June 2002 Meters • Profiling Interval June 2002 N >S Net g.w. flow direction Vertical Exaggeration = 2 € 1 5000+ ug/l* 500 • 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* * Naphthalene Contours June 2002 Figure 4.1.4.1 pH June 2002 81 •9 •6 •5 •5 * e •6 •5 •5 •6 • 10 • 4 •4 •5 •5 •5 •7 • 11 •6 •5 » 4 * 5 • 6 •5 • 5 • 5 • 6 • • 11 • 10 • 13 N Vertical Exaggeration = 2 ->S Net g.w. flow direction Meters Profiling Interval June 2002 W 5000+ ug/l* 41 500 - 5000 ug/r 50 - 500 ug/l* 5- 50 ug/l* Naphthalene Contours June 2002 Figure 4.1.4.2 Alkalinity June 2002 (meq/l) 82 N I I I 1 I I \ I s Fraser River 2£C 984 \ 2477/1 1,319 r * - 228 - 5 0 °" ®~ 5 11 * Naphthalene Contour 1996-1999* (ppb) r\ Inferred extent of Intermediate ^, NAPL** \shoreline \ Cross section A-A' • Profiling Point 1996 • Profiling Point 2002 • Profiling Point 2003 ** Golder 1998 •A-'. . - 5 6 -0 20 40 Meters * Contour of Maximum Naphthalene Concentration Data from Anthony(1998), Bianchin(2001), Lesser(2000) Figure 4.2.1.1 Maximum Naphthalene Concentrations 02-03 (ppb) 83 • Profiling Interval February 2003 N-Vertical Exaggeration = 2 ->S Net g.w. flow direction W 5000+ ug/l* 4f) 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* * Naphthalene Contours February 2003 Figure 4.2.1.2 Naphthalene Concentrations February 2003 84 • N D •20 • 2 7 286* #267 403* •467 •873 •765 • 7 •12 • 6 8 95 • 104 • 94 • 272 • 1 2 8 •266 •700 #-414 Vr/ #" 3 1 5 »33 "348 23 N-Meters Profiling Interval February 2003 -*S Net g.w. flow direction Vertical Exaggeration = 2 €1 5000+ ug/l* 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* * Indane Contours February 2003 Figure 4.2.1.3 Indane Concentrations February 2003 85 Meters • Profiling Interval February 2003 N >S Net g.w. flow direction Vertical Exaggeration = 2 4) 5000+ ug/l* 4) 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* * Naphthalene Contours February 2003 Figure 4.2.1.4 Ratio of Naphthalene to Indane February 2003 (mg/l) 86 Meters • Profiling Interval February 2003 N >S Net g.w. flow direction Vertical Exaggeration = 2 €1 5000+ ug/l* 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* * Benzothiphene Contours February 2003 Figure 4.2.1.5 Benzothiophene February 2003 87 •infinity •infinity • infinity •infinity •2 .5 0.3 • # 0 2 • 0 1 2 : 5 0 »8.0 •7.8 •0.4 9.3 • •4.4 •0.1 •8.7 •2.6 • 0.1 •14.7 •8.1 •0.2 •11.7 •2.4 *0.6 • infinity • 1.0 •1.4 •infinity N-0 3 6 Meters Profiling Interval February 2003 ->S Net g.w. flow direction Vertical Exaggeration = 2 5000+ ug/l* 500 - 5000 ug/l' 50 - 500 ug/l* 5- 50 ug/l* * Naphthalene Contours February 2003 Figure 4.2.1.6 Ratio of Naphthalene to Benzothiophene February 2003 88 N - •*S Net g.w. flow direction Profiling Interval February 2003 Vertical Exaggeration = 2 5000+ ug/l* 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* * Naphthalene Contours February 2003 Figure 4.2.2.1 Iron Concentrations February 2003 (mg/l) 89 •14.6 •13.8 •4 .7 8 . 6 » , 1 2 4 29 # •28.8 27 • •0 .3 •5 .3 19.9* » 2 4 . 9 •13.7 •34.7 •8.2 •8.6 •16.5 • N D • N D •46.6 •46.6 • 39.2 •11.1 •22.7 • N D •7.3 • 1 0 . 2 « 1 . 6 # 3 1 3 • N D •15.2 •10 .3 •20.7 • N D •7 .7 •6.4 0 3 Meters Profiling Interval February 2003 N - ->S Net g.w. flow direction Vertical Exaggeration = 2 5000+ ug/l* 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* * Naphthalene Contours February 2003 Figure 4.2.2.2 Acetate February 2003 (MM) 90 Profiling Interval February 2003 N - ->S Net g.w. flow direction Vertical Exaggeration = 2 5000+ ug/l* 500 • 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* * Naphthalene Contours February 2003 Figure 4.2.3.1 Dissolved Methane February 2003 (mg/l) 91 4) 5000+ ug/l* 4) 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* * Naphthalene Contours February 2003 Figure 4.2.3.2 Dissolved C02 February 2003 (mg/1) Error due to Atmospheric contamination = +/-5.7% 92 Kilometers Fig. 5.1.2.1 Model Grid 93 94 0 0.05 0.1 K i l o m e t e r s Vertical Exagerrat ion = 4 N » S Net g.w. flow direction Figure 5.1.4.1 Conductivity Z o n e s and River Boundary February 1 1 0 1 0.025 0.05 Kilometers June N s - - - - N \j j,/ ^ I 1 1 1 0 0.025 0.05 Kilometers Vertical Exaggeration = 4 Figure 5.1.6.1 Seasonal Variation in Flow Directions 96 Kilom eters Fig. 5.1.7.1 Particle Tracking Results $ Inferred extent of Deep NAPL* \ Railway B Source Containment Well * Golder 1998 r\ Inferred extent of Intermediate w NAPL* \ Shoreline 9 Location of Particle release" "Particles Released June 1999 97 K i l o m ete rs Fig. 5.1.7.1 Particle Tracking Results H Inferred extent of Deep NAPL* \ Railway • Source Containment Well * Golder 1998 r\ Inferred extent of Intermediate <J NAPL* \ Shoreline 9 Location of Particle release** "Particles Released June 1999 97 Fig. 5.1.10.1 Sensitivity Analysis: Particle Tracking Results with Low River Gradient Fig. 5.1.10.2 Sensitivity Analysis: Particle Tracking Results with High River Gradient H Inferred extent of Deep NAPL* * \ Railway B Source Containment Well * Golder 1998 r\ Inferred extent of Intermediate W NAPL* \ Shoreline © Location of Particle release** "Particles Released June 1999 98 Kilometers Fig. 5.1.10.3 Sensitivity Analysis: Particle Tracking Results with Maximum North-South Gradient \ I • J i — i— iri**^ *"* L ^ - — « / / V Z / — 0 0.025 0.05 m kilometers Fig. 5.1.10.4 Sensitivity Analysis: Particle Tracking Results with Minimum North-South Gradient | | Inferred extent of Deep NAPL* \ Railway 1 Source Containment Well * Golder 1998 r\ Inferred extent of Intermediate w NAPL* \ Shoreline 0 Location of Particle release** "Particles Released June 1999 99 O.OOE+00 O.OOE+00 5.00E+07 1.00E+08 1.50E+08 Time (s) Figure 5.2.2.1: Model led vs Field Naphthalene Concentrat ions using a Half Saturat ion Constant of 1x10" 6 1.60E-05 -r 1.40E-05 --1.20E-05 -1.00E-05 --o UJ 8.00E-06 -3 Q 6.00E-06 <» H 4.00E-06 -2.00E-06 -O.OOE+00 -O.OOE+00 2.00E-06 4.00E-06 6.00E-06 8.00E-06 1.00E-05 1.20E-05 Half Saturation Constant Figure 5.2.2.2: Error in fit of model led to field sampled naphthalene concentrat ions for half saturation constants between 1x10" 8 and 1x10"' 100 Compound Detection Limit (u.g/1) Indane * 3 Naphthalene 4 Benzo(b)thiophene * 7 Indole+2-Methyl naphthalene 5 1-Methyl naphthalene 3 Biphenyl 5 Acenaphthylene 3 Acenaphthene 2 Dibenzofuran 3 Fluorene 3 Phenanthrene 6 Anthracene 4 Carbazole >17 Fluoranthene 5 Pyrene 4 B enz(a) anthrac ene >16 Chrysene 6 Benzo(b+k)fluoranthene 20 Benzo(a)pyrene 24 Indeno(l,2,3,c,d)pyrene+dibenz(a,h)anthracene >63 Benzo(g,h,i)perylene >31 * February sampling event only Table 3.2.2.1 Suite of aromatic compounds analyzed Sample Identification Maximum Concentration (ns/i) Naphthalene 2177 Indole+2-Methyl naphthalene 26 1-Methyl naphthalene 86 Biphenyl 20 Acenaphthylene 28 Acenaphthene 25 Dibenzofuran 8 Fluorene 31 Phenanthrene 23 Anthracene 5 Carbazole 0 Fluoranthene 0 Pyrene 4 Benz(a)anthracene 0 Chrysene 0 Benzo(b+k)fluoranthene 0 Benzo(a)pyrene 0 Indeno(l,2,3,c,d)pyrene+dibenz(a,h)anthracene 0 Benzo(g,h,i)perylene 0 Table 4.1.1 Maximum Concentrations Sampled June 2002 102 Sample ID Depth (m) Naphthalene (Ug/l) * PH Alkalinity (meq/1) Iron (mg/1) Nitrate (mg/1) Phosphate (mg/1) Bromide (mg/1) Sulphate (mg/1) Acetate (uM) Chloride (mg/1) Dissolved Methane (mg/1) R02-7-1 6.05 N D 6.9 3.12 N A 0.1 N D N D N D 30 4.5 N D R02-7-2 7.72 N D 6.4 4.04 N A N D N D N D N D N A 5.8 N D R02-7-3 10.5 N D 6.7 5.08 N A 0.1 N D 0.1 N D N A 6.49 1.2 R02-7-4 13.28 N D 6.7 4.52 16.2 N D N D N D N D 28 5 0.8 R02-7-5 16.78 N D 7.6 4.80 N A 0.1 N D N D N D 8 17.5 N D * A l l PAHs analyzed not present NA= Not Analyzed N D = Not Detected Table 4.1.5.1 Uncontaminated Sampling Location 103 Sample Identification Maximum Concentration (ns/i) Indane 873 Naphthalene 2008 Benzo(b)thiophene 163 Indole+2-Methyl naphthalene 17 1-Methyl naphthalene 138 Biphenyl 12 Acenaphthylene 45 Acenaphthene 16 Dibenzofuran 9 Fluorene 20 Phenanthrene 0 Anthracene 0 Carbazole 0 Fluoranthene 0 Pyrene 0 B enz(a) anthr ac ene 0 Chrysene 0 Benzo(b+k)fluoranthene 0 Benzo(a)pyrene 0 Indeno(l,2,3,c,d)pyrene+dibenz(a,h)anthracene 0 Benzo(g,h,i)perylene 0 Table 4.2.1 Maximum Concentrations February 2003 104 Compound Concentration in Concentration in sample sample R03-6-3 (ug/l) R03-5-4 (u.g/1) Indane 71.1 81.3 Naphthalene 6.5 402.1 Benzothiophene 18.9 41.2 Indole+2-Methyl Not Detected 1.7 naphthalene 1-Methyl naphthalene 8.7 5.3 Biphenyl Not Detected Not Detected Acenaphthylene Not Detected 3.3 Acenaphthene Not Detected 1.5 Dibenzofuran Not Detected Not Detected Fluorene Not Detected Not Detected Table 4.2.5 Concentrations of Organic Compounds at Biomarker Sampling Points Gradient Month 1997 1998 1999 Model Input Jan 1.20x10"' N A 4.00x10"" 1.00xl0 J Feb 8.00x10"4 N A 4.00x10"" 6.00x10" Mar 3.00x10-' N A 3.00x10"" 1.86xl0 J Apr 3.00xl0" J 1.00x10"" 1.00x10"" 1.27xlOJ May 5.00xl0"4 6.00x10"' 3.00xl0"4 3.30x10" Jun 5.00x10"" 3.00xl0"4 2.00x10"" 5.00x10" Jul 5.00x10"" 2.00x10"" N A 5.00x10" Aug 5.00x10"" 3.00xl0"4 N A 5.00x10" Sep 5.00x10"" 2.00x10"" N A 5.00x10" Oct 5.00xl0"4 3.00xl0"4 N A 5.00x10" Nov 5.00xl0"4 3.00x10"" N A 5.00x10" Dec 8.00x10"" 4.00x10"" N A 6.00x104 Table 5.1.3.1 Aquifer Gradients 105 Month Recharge (mm/yr) January 301 February 247 March 241 April 279 May 222 June 177 July 127 August 122 September 172 October 256 November 396 December 357 Table 5.1.3.2 Recharge Rates Input to the Groundwater Flow Model Simulation Residence Time of a Particle Released atR96-l* Offshore Flowpaths Low River Gradient 1600 days Particles Discharge to the River High River Gradient 900 days Particles Discharge to the River Low NS Gradient Greater than 1800 days Particles up to 20 metres offshore captured by source containment well along the plume profile High NS Gradient 400 days Particles Discharge to the River * 1400 days in the calibrated simulation. Table 5.1.9.1 Sensitivity Analysis: Summary of Results 106 Parameter Value C a 2 + 19 mg/1 Fe 2 + 49 mg/1 Fe J + 1x10° mg/1 Naphthalene 3.8 mg/1 Alkalinity 4 meq/1 S 0 4 z " 1.1 mg/1 NCV" 0.3 mg/1 o 2 Omg/1 C H 4 6 mg/1 Table 5.2.2 Batch model initial solution Description of Simulation Naph. Deg. Rate Flow Regime Summary of Results Degradation occurs by equal rates of iron reduction and methanogenesis Min. No Source Cont. Reduction in naph. is much lower than observed in 1996. Increases in methane and iron are also lower than observed in 1996. Degradation occurs by equal rates of iron reduction and methanogenesis Max. No Source Cont. Reduction in naph. is somewhat lower than observed in 1996. This is likely due to the initiation of pumping 3 months prior to sampling. Increase in iron is consistent with that observed in 1996. Methane levels are lower than observed in 1996. Degradation occurs by equal rates of iron reduction and methanogenesis Min. Source Cont. Reduction in naph. is lower than observed in recent sampling. Increases in iron, pH, and methane are lower than observed. Degradation occurs by equal rates of iron reduction and methanogenesis Max. Source Cont. Complete degradation of naph. along the flowpath. Increases in iron and pH are consistent with those observed. Methane levels are lower than observed. Degradation of organic matter by methanogenesis Max. Source Cont. Rate of degradation of org. matter by methanogenesis of 3.Ox 10" mol/l-s required to match methane levels observed in the field. pH is slightly lower than observed. Degradation solely by iron reduction Max. Source Cont. Iron levels and pH are much higher than observed in the field. Mineral precipitation (Degradation solely by iron reduction) Max. Source Cont. Iron and pH are much lower than observed in the field. Methane is produced by degradation of organic matter. Surface complexation (Degradation solely by iron reduction) Max. Source Cont. Iron and pH levels are consistent with those observed in the field. Methane is produced by degradation of organic matter. Table 5.2.9.1 Summary of Batch Model Results 108 Appendix Permits FRASER ^PORT FRASER RIVER PORT AUTHORITY 500 • 713 Columbia Street New Westminster, B.C. V3M 1B2 Canada Tel: 604.524.6655' Fax: 604.524.1127 email: fraserport@frpa.com www. fraserportauthority. com File: (022) 021-12-U300-00 CPR: 0205F028 ADMINISTRATION PORTUAIRE DU FLEUVE FRASER 713, rue Columbia, bureau 500 New Westminster (C.-B.) V3M1B2 Canada Te~l: 604.524.6655- Fax: 604.524.1127 courriel: fraserport@frpa.com www. fraserportauthority. com May 27, 2002 ^.j^sdlctlonai Conditions Ms. Christine Bishop University of British Columbia Earth and Ocean Sciences 6339 Stores Rd. Vancouver, BC V6T 1Z4 Dear Ms. Bishop: Re: Environmental Conditions for Proposed Works - Lot D, except firstly, part subdivided by Plan 24152, secondly part subdivided by Plan 42455, thirdly Parcel One (Reference Plan 49372) D.L. 16, Group 1, N.W.D. Plan 4724 and Lot 65, D.L. 16, Group 1, N.W.D. Plan 42455 In the absence of the Municipality talcing a lead role in the Lower Fraser Region, this responsibility of Lead Agency has rested with the Fraser River Port Authority. Therefore the above noted application was reviewed for the proposed works and is subject to the conditions set out in the attached Environmental Review Committee (ERC) letter from the Fraser River Estuary Management Program (FREMP) dated May 9, 2002. The Port Authority's review of the application has been to determine environmental impacts, the type of works, location and possible impact on navigation. The Port Authority has not approved any Geotechnical, Architectural or Engineering aspects of the project. It is your responsibility to ensure the plans, specifications and inspections comply with all applicable Federal, Provincial and Municipal requirements. You are also required to comply with all regulations made by insurance underwriters, governing your occupation of said premises. Progress\oig^f|rm\env_cond itions_ltr.doc Canada E s t u a r y M a n a g e m e n t P r o g r a m F r a s e r R i v e r F R A S E R RIVER PORT AUTHORITY MAY 1 k 2002 Fraser River Port Authority Facs: 604.524.1127 500-713 Columbia Street New Westminster, BC V3M 1B2 Attention: Peg Brownie RE: FREMP 0205F028; Domtar Inc. on Behalf of the University of British Columbia, Application for Environmental Sediment Testing at 25 Braid Street, Coquitlam, BC PROJECT REVIEW Reference is made to the above project proposal referred to the Fraser River Estuary Management Program (FREMP) Environmental Review Committee (ERC) on May 8, 2002 for a coordinated project review. The ERC's review has been based on documents and correspondence that have been submitted by the Port Authority on behalf of the proponent, Domtar Inc. on behalf the University of British Columbia. These documents and correspondence, along with a summary of the ERC's understanding of what works constitute the project, are listed by title and date in Schedule "A" attached to this letter. Should Schedule "A" not reflect accurately the project the proponent intends to undertake, it is the responsibility of the proponent to so advise the ERC. Failure to do so could invalidate this environmental assessment and any subsequent project approvals. It is the conclusion of the ERC that the potential adverse environmental effects of this project can be mitigated through the implementation of appropriate mitigation measures, including (but not necessarily limited to) those recommended below. The ERC has reached its conclusion regarding the environmental effects of the projects based on the expectation that these recommendations will be followed as a minimum. The responsible authorities may therefore proceed to exercise any powers or perform any duties or functions that would permit the project to be carried out on the basis of this advice. The E R C should be notified in advance of any proposed departures from the advice contained in this letter, so that the ERC may determine if the above conclusion remains valid. The conclusions of the environmental assessment are valid until August 8, 2003. After that date, these recommendations and the associated environmental assessment conclusion will be void, no longer valid. Prior to that date, should the proponent substantially alter the project or indicate an intention to depart from the following recommendations, the ERC should be notified as a new assessment will be required in order to determine the continuing validity of the ERC's environmental assessment recommendations. 5945 Kathleen Avenue # 501 Burnaby BC V5H 4J7 • Phone: 604.775.5756 • Fax: 604.775.5198 • www.bieapfremp.org FRPA FREMP CPR # 0205F028 09/05/02; page 3 Due diligence is required at all times to prevent such discharges, and adherence to the terms and conditions of this condition does not of itself relieve Domtar Inc. of this ongoing obligation. 11. The works shall be carried out in such a manner so as to avoid any adverse impact on fish or fish habitat. If the harmful alteration, disruption or destruction of fish habitat occurs, the works will be in contravention of Section 35 of the Fisheries Act. If any such alteration occurs Fisheries and Oceans Canada reserves the right to immediately suspend or alter operations and the proponent and/or their agent(s) or contractor(s) shall undertake, at their own expense, any remedial works deemed necessary by Fisheries and Oceans Canada to ensure a "no net loss" in the productive capacity of local fish habitat. 12. The Field Supervisor, DFO Conservation and Protection, Fraser Valley West (tel. 604-607-4150 or fax 604-607-4199), and Brian Naito DFO Habitat Management (tel. 604-666-8190 or fax 604-666-6627) are to be notified at least five (5) days prior to the start of the proposed works. 13. It is understood that by proceeding with these works, Domtar Inc. and/or its agents and/or contractors shall have indicated that they understand and have agreed to the foregoing conditions. In this regard, a copy of this ERC letter of advice regarding this project is to be provided to any contractor(s) prior to work commencing. In addition, a copy of this ERC letter of advice is to be retained on site at all times when the subject works are underway. The proponent, Domtar Inc., should be advised that the above mitigation measures are recommended on the basis of the ERC's environmental assessment of its project proposal, and form the basis of the ERC's environmental assessment conclusions. The implementation of these mitigation measures may not be adequate to satisfy all the requirements of applicable federal and provincial legislation. Notwithstanding the conclusions and recommendations arising from this environmental assessment, the proponent must obtain all necessary statutory and regulatory approvals for this project, and comply with all applicable requirements under federal and provincial law. Should you have any questions or require further information, please do not hesitate to contact the undersigned at 604-775-5195. Sincerely, Environmental Per: ^Daijia Has/elr^ann Project Review Coordinator Cc: M. Willcox, Ministry Water, Land and Air Protection B. Naito, Fisheries and Oceans A. Duncan, Environment Canada J. Mackie, C C G - N W P A j Al/VHORtTV F r a S e r j HOT 2 $ 2002 R i v e r Jj E s t u a r y — _ M a n a g e m e n t F R E M P P r o g r a m November 19, 2002 Fraser River Port Authority Facs: 604.524.1127 500-713 Columbia Street New Westminster, BC V3M 1B2 Attention: Peg Brownie RE: FREMP CPR# 0211F079; Application Submitted by Christine Bishop, University of British Columbia for Research to Obtain Groundwater Samples at the Stella Jones Facility located at 25 Braid Street, Coquitlam, BC Reference is made to the above subject application submitted to the Fraser River Estuary Management Program (FREMP) Environmental Review Committee (ERC) for a coordinated environmental review. Reference is also made to the letter and application received from the Peg Brownie, Fraser River Port Authority (FRPA) dated November 7, 2002. From the information provided, the FREMP ERC understands that Christine Bishop, University of British Columbia (UBC) Earth and Ocean Sciences proposed is proposing to perform offshore groundwater sampling to investigate the migration of the contamination plume and the offshore tracer of 14C-naphthalene injected in 1999 at 25 Braid Street in Coquitlam. These works are similar in nature to the works reviewed under CPR #0205F028. This proposed sampling round will be specifically applied to determine the cause of reduced containment concentrations observed in the portion of the aquifer beneath the Fraser River in June 2002. The locations of the proposed sampling sites are adjacent to an area of "moderate biological productivity and diversity" or a "Yellow" section of the Fraser River, as coded under the FREMP Habitat Inventory Mapping. Projects within yellow coded sections of the Fraser River may occur provided that mitigation and/or compensation measures are incorporated into the project design to ensure that there is NO NET LOSS of the productive capacity as a result of the project. On the understanding that the foregoing points accurately reflect the subject proposal, it is the opinion of the FREMP ERC that the potential adverse impacts to fish, wildlife and their habitats associated with the proposed works can be mitigated through the application of appropriate criteria. In addition to those measures set out in the information provided, the following measures are intended to prevent or avoid any potentially harmful effects to fish, wildlife and their habitats: 1. Christine Bishop acknowledges that all plans and specifications relating to the works have been duly prepared and reviewed by appropriate professionals working on their behalf. Christine Bishop further acknowledges that it is solely responsible for all design, safety and workmanship aspects of the works. 5945 Kathleen Avenue # 501 Burnaby BC V5H 4J7 • Phone: 604.775.5756 • Fax: 604.775.5198 • www.bieapfremp.org FRPA FREMPCPR#0211F079 Nov. 19,2002; page 2 2. Christine Bishop must ensure that all work associated with the subject project complies with the requirements of the Fisheries Act and any other applicable laws and regulation. 3. Christine Bishop should be reminded of its obligation to comply at all times with Section 36 of the Fisheries Act, which specifically prohibits the discharge of substances deleterious to fish or other aquatic life onto the intertidal foreshore of or into fish-bearing waters such as the Fraser River. Due diligence is required at all times to prevent the discharge of deleterious substances, and adherence to the terms and conditions suggested herein does not of itself relieve Christine Bishop of this ongoing obligation 4. A l l works must be carried out in a manner that minimizes the direct or indirect release of sediment or sediment laden water onto the intertidal foreshore of or into the waters of the Fraser River. In this regard, reference should be made to the water quality criteria for particulate matter as described in the British Columbia Water Quality Guidelines (Criteria): 1998 Edition produced by BC Ministry of Environment, Lands and Parks. 5. Al l works must be undertaken and completed in such a manner so as to prevent the release of substances deleterious to fish and other aquatic life (including, but not limited to, debris, gasoline, oil, grease, etc.) onto the upland and/or intertidal foreshore of or into any watercourse. Furthermore, all waste materials requiring disposal must be disposed of at an authorized upland disposal site. 6. Water-based machinery or equipment (e.g., barges, etc.) shall be located and firmly moored in deep water, far enough offshore to prevent any grounding on the foreshore or bed of the Fraser River. The only exception to this condition is that use may be made of vertical spuds to hold barge(s) in place. 7. There is to be NO disturbance to the riparian vegetation or to the intertidal foreshore located at the subject site. 8. There should be no fuelling or storage of petroleum products on or adjacent to the foreshore associated with the proposed works. Al l petroleum products (e.g., fuel, oil, lubricants), used in association with the construction of the subject works should be stored and handled at an appropriate upland location and in compliance with all applicable legislation, guidelines, and Best Management Practices. 9. An appropriate spill prevention, containment, and clean up contingency plan for hydrocarbon products (e.g., fuel, oil, hydraulic fluid, etc.), and other deleterious substances, and contaminants should be put in place prior to work commencing, and appropriate spill containment and cleanup supplies should be kept available onsite throughout the course of the construction of the subject works. 10. Christine Bishop should be reminded of its obligation to comply at all times with Section 36 of the Fisheries Act, which specifically prohibits the discharge of substances deleterious to fish or other aquatic life onto the intertidal foreshore of or into fish-bearing waters such as the Fraser River. Due diligence is required at all times to prevent such discharges, and adherence to the terms and conditions of this condition does not of itself relieve Christine Bishop of this ongoing obligation. 11. The works shall be carried out in such a manner so as to avoid any adverse impact on fish or fish habitat. If the harmful alteration, disruption or destruction of fish habitat occurs, the works will be in contravention of Section 35 of the Fisheries Act. If any such alteration occurs Fisheries and Oceans Canada reserves the right to immediately suspend or alter operations and the proponent and/or their agent(s) or contractor(s) shall undertake, at their own expense, any remedial works FRPA FREMP CPR # 0211F079 Nov. 19,2002; page 3 deemed necessary by Fisheries and Oceans Canada to ensure a "no net loss" in the productive capacity of local fish habitat. 12. The Field Supervisor, DFO Conservation and Protection, Fraser Valley West (tel. 604-607-4150 or fox 604-607-4199), and Brian Naito DFO Habitat Management (tel. 604-666-8190 or fax 604-666-6627) are to be notified at least five (5) days prior to the start of the proposed works. 13. It is understood that by proceeding with these works, Christine Bishop and/or its agents and/or contractors shall have indicated that they understand and have agreed to the foregoing conditions. In this regard, a copy of this ERC letter of advice regarding this project is to be provided to any contractor(s) prior to work commencing. In addition, a copy of this ERC letter of advice is to be retained on site at all times when the subject works are underway. This letter of advice is valid until November 15, 2003. After this time, if the subject works have not been completed, this letter will be void. This will ensure that the proposed works will conform to current habitat management policy, guidelines, and legislation. Please note that this letter of advice should not be taken to imply approval of the subject works in accordance with the habitat protection provisions of the Fisheries Act or any other federal or provincial legislation. If harmful alteration, disruption or destruction of fish habitat occurs as a result of a change in the plans for the subject proposed works, or failure to implement the additional measures specified above, contravention of subsection 35(1) of the Fisheries Act could occur. Should you have any questions or require further information, please do not hesitate to contact me at Tel: (604) 666-8190. Sincerely, F R E M P Environ Cc: M. Willcox, Ministry Water, Land and Air Protection J. Mackie, Fisheries and Oceans CCG NWPA B. Naito, Fisheries and Oceans A. Duncan, Environment Canada Appendix B: Description of Analyi ORGANIC GEOCHEMISTRY LABORATORY DEPARTMENT OF EARTH SCIENCES Telephone: 519 888 4567 ext. 5180/6370 (written by Marianne Vandergriendt) VOLATILE AND SEMI VOLATILE AROMATIC HYDROCARBON ANALYSIS ( B E N Z E N E , T O L U E N E , E H T Y L B E N Z E N E , p + m - X Y L E N E , o - X Y L E N E , T R I M E T H Y L B E N Z E N E S (1,3,5; 1,2,4 A N D 1,2,3), N A P H T H A L E N E , INDOLE+2-M E T H Y L N A P H T H A , 1 - M E T H Y L N A P H T H A L E N E , B I P H E N Y L , A C E N A P H T H Y L E N E , A C E N A P H T H E N E , D I B E N Z O F U R A N , F L U O R E N E , P H E N A N T H R E N E , A N T H R A C E N E , C A R B A Z O L E , F L U O R A N T H E N E , P Y R E N E , B E N Z O (a) A N T H R A C E N E , C H R Y S E N E , B E N Z O (b+k) F L U O R A N T H E N E , B E N Z O (a) P Y R E N E , I N D E N O (1,2,3,cd) P Y R E N E and D I B E N Z O (a,h) A N T H R A C E N E , A N D B E N Z O (g,h,i) P E R Y L E N E ) INTRODUCTION: A gas chromatographic technique is descr ibed to determine volatile aromatic components of gasol ine and some polycycl ic aromatic components of creosote, in groundwater samples (the components are listed above). Typically, these compounds are determined by purge and trap or exhaustive extraction techniques. However, because the hydrogeologist may require many ana lyses to define the shape, movement and attenuation of a trace contaminant plume, purge and trap methods are too time consuming to use on a routine basis. Separatory funnel or continuous solvent extraction techniques are not only s low and labour intensive but can also suffer from volatilization losses. The methodology presented here was derived from an extraction previously descr ibed by Henderson et. al.(1976). The technique required that the partitioning of the analyte be at equilibrium between the two phases , as opposed to being exhaustively extracted from the water. APPARATUS: Aqueous groundwater samples and methanolic standards are extracted in 18 ml crimp-top hypovials with Tef lon® -faced si l icone septa. The determinations are performed on a gas chromatograph equipped with a split less injection port, a 0.25mm X 30M glass D B 5 capillary column with a film thickness of 0.25um and a f lame ionization detector. The chromatographic condit ions are as follows: injection port temperature, 275°C; initial column temperature, 35°C; initial time, 0.5 min.; heating rate, 15°C/min.; final temperature, 300°C; final t ime, 10.0 m i n . ; detector temperature, 325°C; column flow rate, 3 ml/min hel ium. PROCEDURE: \)SAMPLE BOTTLE PREPARATION. Bottles and other g lassware are soaked in a commercial alkaline cleaning solution for several hours, then rinsed with deionized water, dilute nitric ac id, and more deionized water. The bottles are then baked overnight at 110°C 119 \\)SAMPLE COLLECTION AND HANDLING. Each 18 ml hypovial sample bottle is filled without headspace, quickly crimp sealed with a Teflon septa and then stored at 4°C until extracted (7-14 day time limit). Prior to capping, sodium azide (200ul of a 10 % solution) may be added to the sample bottle as a preservative, if analysis will not occur with 7days. To solvent extract a sample (or standard), the septum cap of the vial is quickly removed and 2.0 ml of water is removed with a syringe. This is followed by the addition of 1.0 ml of dichloromethane, containing the internal standards m-fluorotoluene and 2-fluorobiphenyl. The vial is quickly resealed and agitated on its side at maximum speed (350 rpm) on a platform shaker for 15 min. After shaking, the vial is inverted and the phases are allowed to separate for 10 to 30 minutes. Approximately 0.7ml of the dichloromethane phase is removed from the inverted vial with a syringe (through the septum) and placed in a sealed autosampler vial for injection into the gas chromatograph. \\\)QUALITY CONTROL. Samples and standards are equilibrated to room temperature (approx. 22°C) before extraction. A calibration is made in internal standard mode and standards are run in triplicate at four different levels (or more) covering the expected sample range. A multiple point linear regression is performed to determine linearity and slope of the calibration curve. Standards are prepared by spiking water with a concentrated methanolic stock standard, and are extracted in the same manner as samples. Three methanolic stock standards are used, each an order of magnitude above the other. The methanolic stock standard is prepared gravimetrically, injecting the various pure compounds through a septum into one 60 ml aliquot of methanol, or are purchased commercially. Matrix spikes are performed by spiking a known amount of mid-range standard into a duplicate field sample and then calculating the amount recovered after extraction. Reagent water blanks are run on a daily basis. The methanolic stock standards are stored in a freezer when not in use and are replaced when accuracy becomes unacceptable. Method Detection Limit Aug 4, 1999 Units are pg/L (ppb) N Xo X S MDL benzene toluene ethylbenzene p+m-xylene o-xylene 1,3,5-trimethylbenzene 1,2,4-trimethylbenzene 1,2,3-trimethylbenzene 9 9 9 9 9 9 9 9 23.91 28.82 1.29 3.72 22.55 27.91 3.53 10.22 22.82 25.34 1.26 3.64 45.64 49.56 1.99 5.76 23.64 25.66 1.03 3.00 23.64 26.05 0.84 2.43 23.36 25.28 0.85 2.45 24.72 26.18 0.86 2.49 120 naphthalene 9 15.69 16.93 1.50 4.34 indole+2-methyl naphthalene 9 31.25 24.67 1.61 4.66 1-methyl naphthalene 9 15.69 16.89 0.93 2.68 biphenyl 9 30.44 33.07 1.66 4.80 acenaphthylene 9 15.69 17.00 0.92 2.67 acenaphthene 9 15.63 19.21 0.78 2.27 dibenzofuran 8 15.46 14.89 0.89 2.68 fluorene 9 15.69 18.14 0.92 2.67 phenanthrene 9 15.69 17.69 2.23 6.45 anthracene 9 15.69 16.12 1.25 3.63 carbazole 8 16.87 13.44 1.58 4.74 fluoranthene 9 15.69 18.82 1.79 5.17 pyrene 9 15.63 19.26 1.49 4.30 B(A)anthracene 8 15.63 10.91 1.09 3.26 chrysene 8 15.69 22.42 2.10 6.30 B(b+k)fluoranthene 8 31.25 16.88 6.71 20.11 B(a)pyrene 8 15.69 10.29 8.14 24.40 indeno(1,2,3,c,d)pyrene+dibenzo(a h)anthracene 9 62.63 >62.63 benzo(g,h,i)perylene 9 31.38 >31.38 N= Samp le S ize X o = True Va lue of Standard X = Average Calculated Va lue of Standards S = Standard Deviation M D L = Method Detection Limit N D = Not Detected L I T E R A T U R E C I T E D . Henderson , J . E . , G . R . Peyton and W . H . G l a z e (1976). A convenient liquid-liquid extraction method for the determination of ha lomethanes in water at the parts-per-bil l ion level. IN: Identification and analys is of organic pollutants in water. Kei th, L .H. ed . A n n Arbor S c i e n c e Publ ishers Inc., A n n Arbor, M l . 121 Biomarker Report (Written by Shirley Chatten) Sample Preparation Samples submitted were extracted (3 X 60 ml with methylene chloride) and concentrated using a modification of EPA method #3510C (in duplicate - A , B). For sample A only the acid fraction was extracted, but in sample B an initial clean-up step was used by extracting the B / N fraction and discarding the solvent. The pooled solvent (acid fraction only) was dried under a stream of prepurified nitrogen and reconstituted in 0.5ml methylene chloride (containing 4-fluoro-l-naphthoic acid as an internal standard) prior to derivatizing with BSTFA as outlined in Phelps et al. Samples R03-3-4 and R03-6-3 were injected into a GC/MS and analyzed for naphthalene degradation products. Commercial standards for 2-naphthoic acid (2-NA) and 4-methy-l-naphthoic acid (MNA) were prepared and analyzed to determine retention time (RT) and spectra for comparison. Results 2-NA was not detected in either sample. M N A was found (RT and mass spectrum match) in sample B (<2 ug/L) for both R03-3-4 and R03-6-3 but not in sample A. Another mass spectrum matching that of M N A was found in all samples (A and B), but the retention time was slightly different than that of the M N A standard (Table 1). This could possibly be a different isomer of M N A ? The chromatograms produced from both samples were manually scanned for spectra which matched those of any of the breakdown products dihydo-2-naphthoic acid, 5,6,7,8-tetrahydro-2-naphthoic acid (TH-2-NA) through to decalin 2-carboxylic acid (D-2-CA). Spectra published in Phelps et al., were used as a comparison and guide. Several peaks were found that had spectrum similar to those published. Two spectra matching TH-2-N A were found, as well as one for each of HH-2-NA and OH-2-NA. However, positive confirmation for the presence of these compounds can not be determined from the spectra alone. Retention times (RT) are also required for confirmation. Since none of these compounds are available commercially, this is a difficult task. Using information obtained from e-mail correspondence with Craig Phelps (i.e. retention times of some of the compounds he found), most of the peaks with matching spectra do not elute at the times predicted for the compounds of interest. One of the peaks corresponding to TH-2-N A is a possible match. Further Investieation The next step forward would be to synthesize 5,6,7,8-TH-2-NA and possibly DC-2-NA (note: no spectrum was found for this compound) as outlined in Zhang et al., to positively identify the presence of 5,6,7,8-TH-2-NA by matching both RT and spectra. However, since 2-NA was not detected in either submitted sample, further investigation may not be necessary. 122 Table 1 Compound RT R03-3-4 A No B/N extraction Ac id fraction only extracted R03-3-4B B/N and Ac id fractions extracted B/N d iscarded R03-6-3 A No B/N extraction Ac id fraction only extracted R03-6-3 B B/N and Ac id fractions extracted B /N d iscarded 2 - N A ( S T A N D A R D match) 13.83 N D N D N D N D M N A ( S T A N D A R D match) 14.95 N D < 2ug/L (21221) N D < 2ug/L (19922) M N A ( isomer?) spectrum match 14.82 Detected (26482) Detected (17881) Detected (34325) Detected (28952) D H 2 N A unknown N D N D N D N D T H 2 N A spectrum match Phe lps RT=12.62 12.69 Detected (35114) Detected (26445) Detected (35546) Detected (25765) T H 2 N A spectrum match 13.57 Detected Detected Detected Detected H H 2 N A spectrum match Phe lps RT=12.2 13.77 Detected (46347) Detected (41966) Detected (27281) Detected (22323) O H 2 N A spectrum match Phe lps RT=? 14.87 Detected Detected Detected Detected D 2 C A unknown N D N D N D N D 123 Legend B / N - base, neutral 2-NA - 2-Naphthoic Acid M N A - Methyl-Naphthoic Acid DH2NA - Dihydro-2-Naphthoic Acid TH2NA - Tetrahydro-2-Naphthoic Acid HH2NA - Hexahydro-2-Naphthoic Acid OH2NA - Octahydro-2-Naphthoic Acid D2CA - Decalin-2-Carboxylic Acid ( ) - relative abundance of compounds, value represents the mass abundance of one diagnostic fragment (2NA=229, TH2NA=233, HH2NA=235) References Phelps, C , Battistelli, J., Young, L. (2002) Metabolic biomarkers for monitoring anaerobic naphthalene biodegradation in situ. Environmental Microbiology 4(9), 532-537. Zhang, X . , Sullivan, E., Young, L. (2000) Evidence for aromatic ring reduction in the biodegradation pathway of carboxylated naphthalene by a sulfate reducing consortium. Biodegradation 11: 117-124. 124 Dissolved Gases Analysis Although the dissolved gas sampling techniques used varied between sampling rounds, both techniques rely on equilibration of sample water with a known amount of the carrier gas of the GC. In the first sampling round, the carrier gas of the GC that was used is Argon. In the second sampling round, the carrier gas of the GC that was used is Helium. Once the sample water had equilibrated with the injected gas, a portion of the gas phase was withdrawn and injected into the GC. The partial pressures of CO2 and methane in the gas phase were then recorded. To convert the partial pressure recorded into the initial concentrations of dissolved methane and CO2 in the water sample the following relationships described by Johnson et al. (1990) were utilized. Because the initial concentrations of methane and CO2 in the injected gas are equal to zero, the following equation can be used to relate the initial concentration of a dissolved gas to the concentration measured in the gas phase after equilibration. C°Vl=Cyi + CgVg (Eq.E.l) where C° is the initial concentration of the methane or CO2 in the water, Vg is the volume of the carrier gas injected, Vl is the volume of sample water, Cg is the concentration of methane or CO2 in the gas phase after equilibration, and C! is the concentration of methane or CO2 in the sample water after equilibration. C, can be related to Cg by the following equation C, = KHRTCg (Eq. E.2) where KH is the Henry's Law constant in M/atm, R is the ideal gas constant, and T is the temperature. Combining equations E . l and E.2, the initial concentration of methane or CO2 in the sample can be expressed as 125 q = KRTJ V ^ KHRT + — (Eq. E.3) where P is the partial pressure of methane in the gas phase measured by the GC. Because the GC used in the first round of sampling was set to assume that the sum of the partial pressures of the gases it was calibrated to analyze for was equal to one, an additional adjustment of this data had to be performed to account for the partial pressure of the carrier gas in the injected gas phase. Because the initial concentration of the carrier gas in water is assumed to be near zero, the initial concentration of the carrier gas in the gas phase can be related to the concentrations of the carrier gas after equilibration by the following relation. C;VG=C,VL+CGVG (Eq.E.4) Substituting equation E.2 into E.4 and rearranging the concentration of the carrier gas in the gas phase after equilibration can be expressed as C2 = ^ (Eq. E.5) 8 RT(KHRTV, + VG) Using the Henry's law constant for argon, the carrier gas of the GC, the partial pressure of argon in the gas phase is .71; therefore the sum of the partial pressures of all other gases is equal to .29. For this reason, all gas partial pressure output by the GC were multiplied by this correction factor in the first sampling round. References Johnson, K. M . , Hughes, J.E., Donoghay, P.L., and Sieburth, J .M. 1990. Bottle-Calibration Static Head Space Method for the Determination of Methane Dissolved in Seawater. Analytical Chemistry. 62: 2408-2412 126 Appendix C: Organics June 2002 ORGANIC GEOCHEMISTRY LABORATORY (tel. 519-888-4567 X518076370) Client: Christine Bishop c/o Roger Beckie UBC Laboratory Number: 020604 BTEX, PAH ANALYSIS Analysis occurred on June 24 to June28„ 2002 Analyst: Marianne VanderGriendt (x5180) Units are ug/L (micrograms per liter )(pob) Note: Last two rows are peak area only! Sample Identification MDL 2-1-1 2-2-1 2-2-2 2-2-3 2-2-4 2-2-5 2-2-6 2-2-7 2-2-8 2-2-9 2-2-10 2-3-1 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-Naphthalene 4.34 0 0 5 2 7 228 1090 2177 380 8 5 0 lndole+2-Methyl naphthalene 4.66 0 0 0 2 4 4 8 26 6 0 0 0 1-Methyl naphthalene 2.68 0 0 0 8 19 41 69 86 51 0 0 0 Biphenyl 4.80 0 0 0 0 0 3 7 20 13 0 0 0 Acenaphthylene 2.67 0 0 0 0 8 15 18 28 14 14 12 0 Acenaphthene 2.27 0 0 0 0 5 10 13 25 7 . 0 2 0 Dibenzofuran 2.68 0 0 0 0 0 6 8 7 8 0 0 0 Fluorene 2.67 0 0 0 0 0 6 12 31 0 0 0 0 Phenanthrene 6.45 0 0 0 0 0 2 4 23 15 0 0 0 Anthracene 3.63 0 0 0 0 0 0 0 0 0 0 0 0 Carbazole 4.74 0 0 0 0 0 0 0 0 0 0 0 0 Fluoranthene 5.17 0 0 0 0 0 0 0 0 0 0 0 0 Pyrene 4.30 0 0 0 0 4 0 0 0 0 0 0 0 Benz(a)anthracene 3.26 0 0 0 0 0 0 0 0 0 0 0 0 Chrysene 6.30 0 0 0 0 0 0 0 0 0 0 0 0 Benzo(b+k)fluoranthene 20.11 0 0 0 0 0 0 0 0 0 0 0 0 Benzo(a)pyrene 24.40 0 0 0 0 0 0 0 0 0 0 0 0 lndeno(1,2,3,c,d)pyrene+dibenz(a,h)anthracene >62.63 0 0 0 0 0 0 0 0 0 0 0 0 Benzo(g,h,i)perylene >31.38 0 0 0 0 0 0 0 0 0 0 0 0 Peak area at RT 6.219 (Mass Spec Identified as Indane) 0 33545 6402 12437 57314 134390 213566 279054 244111 8612 834 42411 Peak area right after naphthalene RT 7.965 0 0 0 0 0 18638 33580 47247 20093 547 . 0 0 MDL= METHOD DETECTION LIMIT NA= NOT ANALYZED ZERO = NOT DETECTED GC = GAS CHROMATOGRAPH DUP = DUPLICATE 128 ORGANIC GEOCHEMISTRY LABORATORY (tel. 519-888-4567 X5180, Client: Christine Bishop c/o Roger Beckie UBC Laboratory Number: 020604 BTEX, PAH ANALYSIS Analysis occurred on June 24 to June28„ 2002 Analyst: Marianne VanderGriendt (x5180) Units are uq/L (micrograms per liter l(ppb) Note: Last Sample Identification Naphthalene lndole+2-Methyl naphthalene 1-Methyl naphthalene MDL 2-3-2 2-3-3 24-Jun-02 24-Jun-02 4.34 1 6 4.66 0 0 2.68 2 15 Biphenyl 4.80 0 0 Acenaphthylene 2.67 0 11 Acenaphthene 2.27 0 5 Dibenzofuran 2.68 0 0 Fluorene 2.67 0 0 Phenanthrene 6.45 0 0 Anthracene 3.63 0 0 Carbazole 4.74 0 0 Fiuoranthene 5.17 0 0 Pyrene 4.30 0 0 Benz(a)anthracene 3.26 0 0 Chrysene 6.30 0 0 Benzo(b+k)fluoranthene 20.11 0 0 Benzo(a)pyrene 24.40 0 0 lndeno(1,2,3,c,d)pyrene+dibenz(a,h)anthracene >62.63 0 0 Benzo(g,h,i)perylene >31.38 0 0 Peak area at RT 6.219 (Mass Spec Identified as Indane) 6939 14735 Peak area right after naphthalene RT 7.965 1350 5111 MDL= METHOD DETECTION LIMIT NA= NOT ANALYZED ZERO = NOT DETECTED GC = GAS CHROMATOGRAPH DUP = DUPLICATE 129 -3(GC dup) 2-3-4 2-3-4 dup 2-3-5 2-3-6 2-3-7 2-3-8 2-4-1 2-4-3 2-4-4 2-4-4(du 4-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-O 6 7 9 2 6 2 0 0 3 5 5 0 0 0 0 0 2 0 0 0 0 0 16 0 30 0 0 0 0 0 13 12 12 0 5 5 0 0 0 0 0 0 0 2 9 6 6 0 0 0 0 0 0 13 13 5 6 6 3 2 0 0 0 0 7 5 0 6 6 0 0 0 0 0 0 0 0 0 14 14 8 0 0 0 0 0 11 13 0 17 23 0 0 0 0 0 0 0 0 5 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 14872 62037 62065 27890 2219 2072 0 7427 16395 48153 46840 5175 12748 13479 1975 0 0 0 0 5874 9636 10066 ORGANIC GEOCHEMISTRY LABORATORY (tel. 519-888-4567 X5180, Client: Christine Bishop c/o Roger Beckie UBC Laboratory Number: 020604 BTEX, PAH ANALYSIS Analysis occurred on June 24 to June28„ 2002 Analyst: Marianne VanderGriendt (x5180) Units are uq/L (micrograms per liter )(ppb) Note: Last Sample Identification MDL 2-4-5 2-5-1 2-5-2 24-Jun-02 24-Jun-02 24-Jun-O Naphthalene 4.34 0 4 7 lndole+2-Methyl naphthalene 4.66 0 0 0 1-Methyl naphthalene 2.68 0 4 20 Biphenyl 4.80 0 0 1 Acenaphthylene 2.67 0 10 18 Acenaphthene 2.27 0 3 5 Dibenzofuran 2.68 0 0 0 Fluorene 2.67 0 0 0 Phenanthrene 6.45 0 0 0 Anthracene 3.63 0 0 0 Carbazole 4.74 0 0 0 Fluoranthene 5.17 0 0 0 Pyrene 4.30 0 0 0 Benz(a)anthracene 3.26 0 0 0 Chrysene 6.30 0 0 0 Benzo(b+k)fluoranthene 20.11 0 0 0 Benzo(a)pyrene 24.40 0 0 0 lndeno(1,2,3,c,d)pyrene+dibenz(a,h)anthracene >62.63 0 0 0 Benzo(g,h,i)perylene >31.38 0 0 0 Peak area at RT 6.219 (Mass Spec Identified as Indane) 361 46560 78760 Peak area right after naphthalene RT 7.965 0 12223 21325 MDL= METHOD DETECTION UMIT NA= NOT ANALYZED ZERO =NOT DETECTED GC = GAS CHROMATOGRAPH DUP = DUPLICATE 130 -2 (GC dup) 2-5-3 2-5-4 2-5-5 2-6-1 2-6-2 2-6-3 2-6-3 (GC dup) 2-6-4 2-6-5 !4-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun 7 2 0 0 2 4 5 5 0 0 0 7 0 0 0 0 0 0 8 0 23 0 0 0 0 9 10 10 0 0 5 0 0 0 0 0 0 2 0 0 18 13 0 0 0 6 10 10 9 0 7 0 0 0 0 3 6 7 0 0 0 0 0 0 0 0 4 4 0 0 0 0 0 0 0 0 6 6 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 78697 7344 0 0 27683 37333 32578 32458 3854 0 21642 1112 0 0 2566 13688 8509 8732 754 0 ORGANIC GEOCHEMISTRY LABORATORY (tel. 519-888-4567 X5180, Client: Christine Bishop c/o Roger Beckie UBC Laboratory Number: 020604 BTEX, PAH ANALYSIS Analysis occurred on June 24 to June28,, 2002 Analyst: Marianne VanderGriendt (x5180) Units are up/L (micrograms per liter )(ppb) Note: Last Sample Identification Naphthalene lndole+2-Methyl naphthalene 1-Methyl naphthalene MDL 4.34 4.66 2.68 2-7-1 2-7-2 2-7-3 2-7-4 2-7-5 Organic Blank Blank-1 Blank-2 Blank-3 Blank-4 Blank-5 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 24-Jun-02 Biphenyl 4.80 0 0 0 0 0 Acenaphthylene 2.67 0 0 0 0 0 Acenaphthene 2.27 0 0 0 0 0 Dibenzofuran 2.68 0 0 0 0 0 Fluorene 2.67 0 0 0 0 0 Phenanthrene 6.45 0 0 0 0 0 Anthracene 3.63 0 0 0 0 0 Carbazole 4.74 0 0 0 0 0 Fluoranthene 5.17 0 0 0 0 0 Pyrene 4.30 0 0 0 0 0 Benz(a)anthracene 3.26 0 0 0 0 0 Chrysene 6.30 0 0 0 0 0 Benzo(b+k)fluoranthene 20.11 0 0 0 0 0 Benzo(a)pyrene 24.40 0 0 0 0 0 !ndeno(1,2,3,c,d)pyrene+dibenz(a,h)anthracene >62.63 0 0 0 0 0 Benzo(g,h,i)perylene >31.38 0 0 0 0 0 Peak area at RT 6.219 (Mass Spec Identified as Indane) 0 0 0 0 0 Peak area right after naphthalene RT 7.965 0 0 0 0 0 MDL= METHOD DETECTION UMIT NA= NOT ANALYZED ZERO = NOT DETECTED GC = GAS CHROMATOGRAPH DUP = DUPLICATE 131 Appendix D: Geochemical Data June 2002 132 Anions uM 3 uS 3 uS 3 uS 3 uS 1uS 30 uS Sample Nitrate Phosphate Bromide Sulphate Acetate chloride Anions Blank 1.2 ND 0.1 ND 1.4 73 R02-2-1 1.5 ND 0.2 1.2 16.3 790 R02-2-2 37.5 ND 1.7 1.1 29.5 137 R02-2-3 1.3 ND 0.5 0.1 11 111 R02-2-4 10.4 ND 0.07 0.1 199.5 64 R02-2-5 0.7 ND 0.23 1.43 253.3 183.7 R02-2-6 31.5 ND 0.2 1.1 12.4 278.5 R02-2-7 11.5 ND 1.1 0.3 12.1 213.9 R02-2-8 44 ND 1 1.9 18.1 136.8 R02-2-9 19.72 ND 5.4 3.5 17.1 114.5 R02-2-10 3.4 ND 2.3 11.6 17.6 1639 R02-3-1 24.1 ND ND 0.1 14.2 271.4 R02-3-2 107.9 ND ND 1.6 18.4 107.4 R02-3-3 0.8 ND ND ND 21.5 97.8 R02-3-4 4.7 ND 1.2 0.3 19.9 254 R02-3-5 0.9 ND 0.7 0.1 18.9 360.4 R02-3-5b 26.2 ND 0.9 4.4 19 not run R02-3-6 112.6 ND 1.2 0.3 39.6 37.5 R02-3-7 4.5 ND 6 0.3 16.1 4144.9 R02-3-8 6.2 ND 2.3 0.1 23 1466.5 R02-4-1 3.7 ND 1.8 0.4 20.7 774.2 R02-4-2 1.1 ND 0.1 0.4 1.4 227.9 R02-4-3 6.3 ND 0.3 0.1 7.6 219.4 R02-4-4 5.2 ND ND 0.1 21.3 129.1 R02-4-5 6.2 ND 14.8 0.1 ND 9394.9 R02-5-1 10.8 ND ND 0.7 19.4 673.4 R02-5-2 AD ND 19.8 ND 27.4 166.5 R02-5-3 47.7 ND ND ND 20.6 603.9 R02-5-3B 104.4 ND ND 0.2 24.4 369.8 R02-5-4 79.8 ND 8.3 0.1 5.7 5758.2 R02-6-2 4.4 ND ND 0.9 26.8 97.7 R02-6-3 6.3 ND ND 0.5 47.3 449.4 R02-6-4 2.1 ND 0.1 0.3 16 248 R02-6-5 29 ND 9 1.2 10.4 3917.3 R02-7-1 1.3 ND ND ND 30.1 127 R02-7-2 0.8 ND 0.2 ND ? 164 R02-7-3 1.6 ND 0.8 ND ? 183 R02-7-3dup not run not run not run not run not run 159 R02-7-4 0.7 ND ND 0.06 28.4 150.8 R02-7-5 1 ND ND ND 8.4 494.9 ND=Not Detected AD=above detection (likely contamination) ?=technical difficulties during analysis Project Domtar 2002 Water Analysis COWI Report to UBC - Earth & Ocean Sciences ALS File No. P6747 Date Received 7/9/2002 Date: 7/25/2002 ALS Sample ID Date Sampled Time Sampled Sample ID Aluminum D-AI Antimony D-Sb Arsenic D-As Barium D-Ba R02-2-2 6/10/2002 11:00 1 <0.2 <0.2 <0.2 0.13 R02-2-4 6/10/2002 15:04 2 <0.2 <0.2 <0.2 0.1 R02-2-5 6/10/2002 15:19 3 <0.2 <0.2 <0.2 0.1 R02-2-6 6/10/2002 16:19 4 <0.2 <0.2 <0.2 0.09 R02-2-7 6/10/2002 16:55 5 <0.2 <0.2 <0.2 0.12 R02-2-8 6/10/2002 17:24 6 <0.2 <0.2 <0.2 0.06 R02-2-10 6/10/2002 18:30 7 <0.2 <0.2 <0.2 0.08 R02-3-1 6/11/2002 12:06 8 <0.2 <0.2 <0.2 0.15 R02-3-3 6/11/2002 13:34 9 <0.2 <0.2 <0.2 0.05 R02-3-6 6/11/2002 16:00 10 <0.2 <0.2 <0.2 0.04 R02-4-1 6/11/2002 18:58 11 <0.2 <0.2 <0.2 0.13 R02-4-3 6/11/2002 21:11 12 <0.2 <0.2 <0.2 0.04 R02-4-5 6/12/2002 20:00 13 <0.2 <0.2 <0.2 0.56 R02-6-1 6/12/2002 17:25 14 <0.2 <0.2 <0.2 0.11 R02-6-2 6/12/2002 18:39 15 <0.2 <0.2 <0.2 0.41 R02-6-4 6/12/2002 20:06 16 <0.2 <0.2 <0.2 0.13 R02-5-1 6/12/2002 13:10 17 <0.2 <0.2 <0.2 0.06 R02-5-3 6/12/2002 14:27 18 <0.2 <0.2 <0.2 0.12 R02-5-4 6/12/2002 15:06 19 <0.2 <0.2 <0.2 0.65 R02-7-4 6/12/2002 10:14 20 <0.2 <0.2 <0.2 0.16 Beryllium Bismuth Boron Cadmium Calcium Chromium Cobalt Copper D-D-Be D-Bi D-B D-Cd D-Ca D-Cr D-Co D-Cu Fe <0.005 <0.2 0.1 <0.01 34.6 <0.01 <0.01 <0.01 41.7 <0.005 <0.2 0.1 <0.01 26.4 <0.01 <0.01 <0.01 47.3 <0.005 <0.2 0.1 <0.01 25.8 <0.01 <0.01 <0.01 48 <0.005 <0.2 0.1 O.01 27 <0.01 <0.01 <0.01 50.8 <0.005 <0.2 0.1 <0.01 26.8 <0.01 <0.01 <0.01 75.8 <0.005 <0.2 0.1 <0.01 29.5 <0.01 <0.01 <0.01 70.7 <0.005 <0.5 0.2 <0.01 121 <0.01 <0.01 <0.01 41.2 <0.005 <0.2 0.2 <0.01 58.8 <0.01 <0.01 0.02 112 <0.005 <0.2 0.1 <0.01 18.9 O.01 <0.01 <0.01 51.5 <0.005 <0.2 0.1 <0.01 57.3 <0.01 <0.01 <0.01 21 <0.005 <0.2 0.3 <0.01 50.1 <0.01 <0.01 <0.01 109 <0.005 <0.2 0.1 <0.01 24.7 <0.01 <0.01 <0.01 54.5 <0.005 <0.2 0.9 <0.01 192 <0.01 <0.01 <0.01 36.9 <0.005 <0.2 0.1 <0.01 37 <0.01 <0.01 <0.01 64.9 <0.005 <0.2 0.1 <0.01 24.8 <0.01 <0.01 <0.01 47.9 <0.005 <0.2 0.1 <0.01 66.7 <0.01 <0.01 <0.01 26 <0.005 <0.2 0.1 <0.01 28.1 <0.01 O.01 <0.01 49.1 <0.005 <0.2 0.1 <0.01 56 <0.01 <0.01 <0.01 24.8 <0.005 <0.2 0.7 <0.01 243 <0.01 <0.01 <0.01 43.4 <0.005 <0.2 <0.1 <0.01 45.9 <0.01 <0.01 O.01 16.2 135 Project Domtar 2002 Water Analysis COWI Report to UBC - Earth & Ocean Sciences ALS File No. P6747 Date Received 7/9/2002 Date: 7/25/2002 Lead Lithium Magnesium Manganese Molybdenum Nickel Sample ID D-Pb D-Li D-Mg D-Mn D-Mo D-Ni R02-2-2 <0.05 <0.01 23.4 0.95 <0.03 <0.05 R02-2-4 <0.05 <0.01 17.7 1.09 <0.03 <0.05 R02-2-5 <0.05 <0.01 17.3 1.14 <0.03 <0.05 R02-2-6 <0.05 <0.01 16.7 1.22 <0.03 <0.05 R02-2-7 <0.05 <0.01 15.6 1.49 <0.03 <0.05 R02-2-8 <0.05 <0.01 13.9 2.25 <0.03 <0.05 R02-2-10 0.07 <0.01 22 2.71 <0.03 <0.05 R02-3-1 <0.05 <0.01 25.1 7!12 <0.03 <0.05 R02-3-3 <0.05 <0.01 11 1.06 <0.03 <0.05 R02-3-6 <0.05 <0.01 19 0.828 <0.03 <0.05 R02-4-1 <0.05 <0.01 25.7 2.78 <0.03 <0.05 R02-4-3 <0.05 <0.01 15.8 1.13 <0.03 <0.05 R02-4-5 <0.05 0.01 27.2 2.56 <0.03 <0.05 R02-6-1 <0.05 <0.01 20 1.42 <0.03 <0.05 R02-6-2 <0.05 <0.01 15.6 0.963 <0.03 <0.05 R02-6-4 <0.05 <0.01 25 1.3 <0.03 <0.05 R02-5-1 <0.05 <0.01 18.8 0.912 <0.03 <0.05 R02-5-3 <0.05 <0.01 18.6 1.31 <0.03 <0.05 R02-5-4 <0.05 0.01 50.3 3.72 <0.03 <0.05 R02-7-4 <0.05 <0.01 16.6 1.54 <0.03 <0.05 Phosphorus Potassium Selenium Silicon Silver Sodium Strontium Thallium Tin D-P D-K D-Se D-Si D-Ag D-Na D-Sr D-TI D-Sn <0.3 <2 <0.2 22.6 <0.01 18 0.172 <0.2 <0.03 <0.3 3 <0.2 17.9 <0.01 20 0.142 <0.2 <0.03 <0.3 <2 <0.2 17.6 <0.01 17 0.143 <0.2 <0.03 <0.3 <2 <0.2 17.8 <0.01 15 0.149 <0.2 <0.03 <0.3 <2 <0.2 19.2 <0.01 13 0.16 <0.2 <0.03 <0.3 <2 <0.2 20.6 <0.01 10 0.182 <0.2 <0.03 <0.5 4 <0.2 20.5 <0.01 9 0.464 <0.2 0.05 <0.3 3 <0.2 21.8 <0.01 19 0.361 <0.2 <0.03 <0.3 <2 <0.2 18.4 <0.01 22 0.121 <0.2 <0.03 <0.3 <2 <0.2 25.1 <0.01 8 0.226 <0.2 <0.03 <0.3 5 <0.2 26.2 <0.01 20 0.237 <0.2 <0.03 <0.3 <2 <0.2 20.1 <0.01 26 0.149 <0.2 <0.03 <0.3 46 <0.2 20.7 <0.01 976 1.18 <0.2 <0.03 <0.3 <2 <0.2 24.1 <0.01 21 0.16 <0.2 <0.03 <0.3 <2 <0.2 20.1 0.01 20 0.124 <0.2 <0.03 <0.3 2 <0.2 24.4 <0.01 8 0.237 <0.2 <0.03 <0.3 <2 <0.2 21.3 <0.01 20 0.141 <0.2 <0.03 <0.3 <2 <0.2 24.4 <0.01 7 0.194 <0.2 <0.03 <0.3 45 <0.2 20.9 <0.01 863 1.51 <0.2 <0.03 <0.3 4 <0.2 20.1 <0.01 12 0.184 <0.2 <0.03 136 Project Domtar 2002 Water Analysis COWI Report to UBC - Earth & Ocean Sciences ALS File No. P6747 Date Received 7/9/2002 Date: 7/25/2002 Titanium Vanadium Zinc Sample ID D-Ti D-V D-Zn R02-2-2 <0.01 <0.03 0.047 R02-2-4 <0.01 <0.03 0.062 R02-2-5 <0.01 <0.03 0.057 R02-2-6 <0.01 <0.03 0.03 R02-2-7 <0.01 <0.03 0.037 R02-2-8 <0.01 <0.03 0.03 R02-2-10 <0.01 <0.03 0.025 R02-3-1 <0.01 <0.03 0.061 R02-3-3 <0.01 <0.03 0.034 R02-3-6 <0.01 <0.03 0.025 R02-4-1 <0.01 <0.03 0.03 R02-4-3 <0.01 <0.03 0.041 R02-4-5 <0.01 <0.03 0.046 R02-6-1 <0.01 <0.03 0.1 R02-6-2 <0.01 <0.03 0.185 R02-6-4 <0.01 <0.03 0.062 R02-5-1 <0.01 <0.03 0.044 R02-5-3 <0.01 <0.03 0.043 R02-5-4 <0.01 <0.03 0.047 R02-7-4 <0.01 <0.03 0.066 Dissolved Gases June 02 Sample ID Partial Pressure C02 Partial Pressure Methane T(oC) CH4 (ppm)* C02 (ppm)* Predicted C02 (mg/l)** R02-2-3 0.063 0.013 15.0 0.389 40.436 149.2 R02-2-4 0.100 0.080 15.0 2.394 64.185 155.0 R02-2-5 0.000 0.160 15.0 4.787 0.000 156.4 R02-2-6 0.000 0.000 15.5 0.000 0.000 156.2 R02-2-7 0.000 0.210 15.0 6.283 0.000 176.2 R02-2-8 0.075 0.082 14.5 2.457 48.146 168.4 R02-2-9 0.000 0.098 15.2 2.931 0.000 86.5 R02-2-10 0.000 0.270 14.5 8.089 0.000 104.3 R02-3-1 0.000 0.130 15.0 3.890 0.000 386.3 R02-3-2 0.000 0.051 15.0 1.526 0.000 266.1 R02-3-3 0.110 0.067 15.0 2.005 70.603 279.7 R02-3-4 0.140 0.030 15.0 0.898 89.859 199.6 R02-3-4 Dup 0.000 0.098 17.5 2.914 0.000 R02-3-5 0.120 0.370 17.5 11.001 76.960 176.9 R02-3-6 0.000 0.280 16.5 8.346 0.000 198.1 R02-3-7 0.000 0.246 14.5 7.370 0.000 216.2 R02-3-8 0.000 0.174 13.0 5.233 0.000 167.1 R02-4-1 0.000 0.000 15.0 0.000 0.000 712.8 R02-4-2 0.000 0.000 15.0 0.000 0.000 115.4 R02-4-3 0.199 0.276 16.5 8.227 127.666 R02-4-4 0.133 0.261 16.5 7.780 85.324 287.5 R02-4-4 Dup 16.5 0.000 0.000 R02-4-5 0.000 0.217 15.5 6.484 0.000 135.8 R02-5-1 17.0 0.000 0.000 122.5 R02-5-2 0.000 0.328 16.0 9.789 0.000 92.7 R02-5-3 0.102 0.315 15.5 9.413 65.458 R02-5-4 0.097 0.151 16.0 4.507 62.239 87.8 R02-5-5 0.000 0.196 17.5 5.827 0.000 23.0 R02-6-1 0.000 0.103 14.5 3.086 0.000 86.9 R02-6-2 0.000 0.232 13.0 6.977 0.000 74.0 R02-6-3 0.000 0.190 14.5 5.692 0.000 127.4 R02-6-4 0.000 0.329 13.0 9.894 0.000 112.6 138 R02-6-5 0.000 0.186 14.0 5.579 0.000 53.2 R02-7-1 0.000 0.000 16.0 0.000 0.000 52.2 R02-7-2 0.000 0.000 15.0 0.000 0.000 160.0 R02-7-3 0.133 0.040 17.5 1.183 85.297 95.4 R02-7-4 0.061 0.027 16.0 0.815 38.883 80.2 R02-7-5 0.000 0.000 14.5 0.000 0.000 10.9 average 15.4 Henry's Law Constants Methane KH = 1.57e-3 M/atm (Stumm and Morgan, 1996) C02 KH = 4.61 e-2 M/atm (CRC Handbook) Volume Gas = 4 ml Volume Liquid = 34 ml * = corrected for the partial pressure of argon ** = predicted from pH and alkalinity data 139 Sample ID Depth (m) T (C) pH Conductivity (uS/m) Br (ppm) Acid Added (ml) Alkalinity (eq/1) R02-2-1 3.36 22.8 6.2 351 2.56 2.27 9.08E-03 R02-2-2 5.31 21.4 6.3 257 1.15 1.44 5.76E-03 R02-2-3 6.92 21.5 6.5 245 2.71 1.2 4.80E-03 R02-2-4 7.64 20.3 6.5 230 6.01 1.23 4.92E-03 R02-2-5 8.2 19.7 6.5 141.7 3.27 1.23 4.92E-03 R02-2-6 8.55 19.8 6.5 140 4.17 1.23 4.92E-03 R02-2-7 9.93 19.3 6.5 138.1 3.75 1.38 5.52E-03 R02-2-8 11.17 18.7 6.5 128.7 4.34 1.31 5.24E-03 R02-2-9 13.42 18.3 6.8 124.9 1.33 5.32E-03 R02-2-10 15.08 18.1 6.8 247 7.95 1.6 6.40E-03 R02-3-1 5.33 20.3 6.4 412 16.8 2.47 9.88E-03 R02-3-2 6.97 20.3 6.2 161.4 19.6 1.06 4.24E-03 R02-3-3 8.9 6.2 213 42.5 1.1 4.40E-03 R02-3-4 10.56 21.4 6.4 232 50.8 1.27 5.08E-03 R02-3-5 12.22 21.3 6.4 142.1 40.5 1.13 4.52E-03 R02-3-6 13.59 21.9 6.4 214 32.9 1.28 5.12E-03 R02-3-7 14.97 22.2 6.5 475 78.2 1.78 7.12E-03 R02-3-8 16.39 21.5 6.8 2630 74.6 2.73 1.09E-02 R02-4-1 6.12 20.1 6.1 575 3.04 2.28 9.12E-03 R02-4-2 7.57 16.5 6.6 277 17.1 1.08 4.32E-03 R02-4-3 8.89 15.6 303 30.1 1.38 5.52E-03 R02-4-4 11.12 14.5 6.3 288 39.3 1.31 5.24E-03 R02-4-5 16.27 19.5 6.8 2410 2.15 8.60E-03 R02-5-1 5.48 24.8 6.6 315 17.4 1.3 5.20E-03 R02-5-2 8.33 25.6 6.7 303 71 1.24 4.96E-03 R02-5-3 11.14 25.3 6.9 301 85.3 R02-5-4 13.32 27 7 2340 192 2.46 9.84E-03 R02-5-5 16.43 26.6 7.7 4300 86.1 3.24 1.30E-02 R02-6-1 4.57 28.1 6.8 389 51.8 1.52 6.08E-03 R02-6-2 6.84 23.7 6.8 291 104 1.22 4.88E-03 R02-6-3 9.3 21.9 6.6 272 107 1.29 5.16E-03 140 R02-6-4 12.21 20.7 6.7 338 1.43 5.72E-03 R02-6-5 15.13 21 7.3 2750 122 2.8 1.12E-02 R02-7-1 6.05 17.2 6.9 263 8.98 0.78 3.12E-03 R02-7-2 7.72 20.3 6.4 267 49.2 1.01 4.04E-03 R02-7-3 10.5 24.9 6.7 327 78.2 1.27 5.08E-03 R02-7-4 13.28 29.5 6.7 295 137 1.13 4.52E-03 R02-7-5 16.78 27.6 7.6 366 29 1.2 4.80E-03 141 Iron (mg/1) •41.7 •112 M7.3 •50.8 »51.5 •75.8 •70.7 '21 •41.2 •64„9 *109 •47.9 *49.' •54.5 •26 ^.oj •43.4| •36.9 Manganese (mg/l) •0.95 •7.12 ?.09 *I22 *106 •1.49 •2.25 •0.83 •2.71 •1.13 •1.3 »1.31 •3.72| •2.56 Calcium (mg/l) *3*50.1 •34.6 " 5 8 8 •24.8 '28.-•24.7 •26.4 * 2 7 »18.9 •26.8 •29.5 •66.7 »56 •57.3 •243 •192 •121 5000+ ug/l* 500 - 5000 ug/l*j 50 - 500 ug/l* 5- 50 ug/l* * Naphthalene Contours June 2002 • Profiling Interval June 2002 0 3 6 N - -»S Net g.w. flow direction Vertical Exaggeration = 2 142 Sodium (mg/1) Potassium (mg/1) Magnesium (mg/1) • 2 0 ^ •25.7 •23.4 ^ •15.6 '18.1 •15.8 •17.7 «16.7 »11 •15.6 •13.9 • 2 5 »18.€ •19 •50.3 •27.2 •22 5000+ ug/l* 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* * Naphthalene Contours June 2002 • Profiling Interval June 2002 N - ->S Net g.w. flow direction Vertical Exaggeration = 2 143 Nitrate (mg/l) •0.09 •0.23 •2.331-49 •0.27 *0.6-•0.08 * 6 6 9 •0.39 *1.95*0.04 •0.39 • •0.32 "0-71 »o.29 Hrtsm •0.13 »2.9( •1 22*6-98 •0.21 'O 2 8 •4.9! •0.38 •0.38 Phosphate (mg/l) •ND •ND •ND •ND •NO * N D •ND •ND •ND IND •ND •ND • ND •ND •ND •ND •ND •ND •ND •ND •ND •ND •ND * • ND *ND •ND •ND Bromide (mg/l) •0.02 •0.14 •0.04 •ND •ND •0.02 *ND •0.09 «o. 10 •° 0 8 -0.06 •0.43*010 ,•0.48 •0.18 •0.18 •0.14 •ND "ND •0.02 •ND «1.5C1 •ND •0.01 • ND •o.eel •1.18 P 5000+ ug/l* 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* * Naphthalene Contours June 2002 • Profiling Interval June 2002 -»S N Net g.w. flow direction Vertical Exaggeration = 2 144 Sulphate (mg/1) Acetate (mg/1) Chloride (mg/1) •0.12 •0.11 'a 0 1 <«0.15 <o!l'l *ND •0 03^.03 •°- 1 8 .o .oi •0.34 "003 , «0.03 •0.04 •0.09 *0-° •0.01 •0.05 »ND •0.01 •0.03 •ND •0.01 •0.01 •1.11 •0.01 128.00 •4.86 •9.62 3-83, * 3 ' 8 1 ^87*3.47 •7-58«9.oo M JN 2 .80 •4.06 "I 3 3 58.10 .146.94 5 1 . 9 9 •27.45 •3.46 ^38f •7.78 •15.93-5.9fJ •458 •8.79 «21.4|l S04. S33.05 5000+ ug/l* 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* * Naphthalene Contours June 2002 • Profiling Interval June 2002 -»S N Net g.w. flow direction Vertical Exaggeration = 2 145 pH • • •" • 6.15 .6.31* 6 4 4 ;8 .46* 6 - 1 7 I 6-4^ 6.15 •6.5 .6.4 • 6- 4 5.6.42 . 6.7?? 6.42 . 6 . 7 / 6 4 5 • 6.77 • 6.07 6*7 * 6.6* • •6.6P • 6.3 • 6.68 • 6.9] • «6.79 • 7.6t Conductivity (microS/m) Alkalinity (meq/l) •351 •257 •412 •161.4 •$3 »140 »213 •138.*232 •128-I 1 4 2 1 •124.9214 •475 •247 •2,630 5000+ ug/l* 500 - 5000 ug/l* 50 - 500 ug/l* 5- 50 ug/l* * Naphthalene Contours June 2002 • Profiling Interval June 2002 '3%75 •291 "31 i •303 •272 »303 •288 •338 »301 •2,34) •2,410 •4,30p 0 3 6 Malar 5 •9 •6 •9 •6 •10 • 5 * •5 •5 •4 •6 •5 •5 •5 *5 •4 ...... «5 •6 •5 •5 •6 • •5 •5 •5 * «9 •10 •6 •7 •11 •13 0 3 6 Meleis N-Net g.w. flow direction Vertical Exaggeration = 2 146 Appendix E: Organics February 2003 ORGANIC GEOCHEMISTRY LABORATORY (tel. 519-888-4567 x5180/6370) Client: Christine Bishop c/o Roger Beckie UBC Laboratory Number: 030202 BTEX, PAH ANALYSIS Analysis occurred on Feb 19 to Feb 28, 2003 Analyst: Marianne VanderGriendt (x5180) Units are ug/L (micrograms per liter )(ppb) Sample Identification MDL R03-1-3 14-Feb-03 Indane 2.98 347.93 Naphthalene 4.34 4.43 Benzo(b)thiophene 6.63 53.57 lndole+2-Methyl naphthalene 4.66 14.12 1-Methyl naphthalene 2.68 110.81 Biphenyl 4.80 2.92 Acenaphthylene 2.67 25.95 Acenaphthene 2.27 16.17 Dibenzofuran 2.68 4.26 Fluorene 2.67 3.99 Phenanthrene 6.45 0.00 Anthracene 3.63 0.00 Carbazole >16.95 0.00 Fluoranthene 5.17 0.00 Pyrene 4.30 0.00 Benz(a)anthracene >15.69 0.00 Chrysene 6.30 0.00 Benzo(b+k)fluoranthene 20.11 0.00 Benzo(a)pyrene 24.40 0.00 lndeno(1,2,3,c,d)pyrene+dibenz(a,h)anthracene >62.63 0.00 Benzo(g,h,i)perylene >31.38 0.00 GC=GAS CHROMATOGRAPH MDL= METHOD DETECTION LIMIT ZERO = NOT DETECTED 148 R03-2-2 14-Feb-03 127.90 3.80 36.71 5.61 6.64 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-3-2 14-Feb-03 95.19 0.00 10.68 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-3-3 14-Feb-03 93.56 15.66 40.19 0.00 6.19 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-3-4 14-Feb-03 266.39 228.16 86.22 0.00 16.17 0.00 7.72 5.77 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Extraction duplicate R03-3-4 14-Feb-03 267.99 233.35 87.54 2.26 16.64 0.00 6.04 2.04 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ORGANIC GEOCHEMISTRY LABORATORY (tel. 519-888-45 Client: Christine Bishop c/o Roger Beckie UBC Laboratory Number: 030202 BTEX, PAH ANALYSIS Analysis occurred on Feb 19 to Feb 28, 2003 Analyst: Marianne VanderGriendt (x5180) Units are ug/L (micrograms per liter )(ppb) Field Duplicate Sample Identification MDL R03-3-4b 14-Feb-03 Indane 2.98 259.11 Naphthalene 4.34 221.29 Benzo(b)thiophene 6.63 83.49 lndole+2-Methyl naphthalene 4.66 0.00 1-Methyl naphthalene 2.68 17.18 Biphenyl 4.80 0.00 Acenaphthylene 2.67 6.13 Acenaphthene 2.27 5.64 Dibenzofuran 2.68 0.00 Fluorene 2.67 0.00 Phenanthrene 6.45 0.00 Anthracene 3.63 0.00 Carbazole >16.95 0.00 Fluoranthene 5.17 0.00 Pyrene 4.30 0.00 Benz(a)anthracene >15.69 0.00 Chrysene 6.30 0.00 Benzo(b+k)fluoranthene 20.11 0.00 Benzo(a)pyrene 24.40 0.00 lndeno(1,2,3,c,d)pyrene+dibenz(a,h)anthracene >62.63 0.00 Benzo(g,h,i)perylene >31.38 0.00 GC=GAS CHROMATOGRAPH MDL= METHOD DETECTION LIMIT ZERO = NOT DETECTED 149 R03-4-1 14-Feb-03 3.50 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-4-2 14-Feb-03 67.94 85.47 33.94 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-4-3 14-Feb-03 104.12 291.98 37.39 0.00 7.73 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-4-4 14-Feb-03 272.16 418.29 95.79 5.18 17.99 0.00 8.71 6.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-4-5 14-Feb-03 699.96 1318.96 162.64 12.20 28.44 5.95 14.88 14.22 6.91 15.40 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ORGANIC GEOCHEMISTRY LABORATORY (tel. 519-888-45 Client: Christine Bishop c/o Roger Beckie UBC Laboratory Number: 030202 BTEX, PAH ANALYSIS Analysis occurred on Feb 19 to Feb 28, 2003 Analyst: Marianne VanderGriendt (x5180) Units are ug/L (micrograms per liter )(ppb) Sample Identification MDL R03-4-6 14-Feb-03 Indane 2.98 17.05 Naphthalene 4.34 8.67 Benzo(b)thiophene 6.63 3.54 lndole+2-Methyl naphthalene 4.66 7.51 1-Methyl naphthalene 2.68 86.31 Biphenyl 4.80 0.00 Acenaphthylene 2.67 7.78 Acenaphthene 2.27 0.00 Dibenzofuran 2.68 0.00 Fluorene 2.67 0.00 Phenanthrene 6.45 0.00 Anthracene 3.63 0.00 Carbazole >16.95 0.00 Fluoranthene 5.17 0.00 Pyrene 4.30 0.00 Benz(a)anthracene >15.69 0.00 Chrysene 6.30 0.00 Benzo(b+k)f I uoranthene 20.11 0.00 Benzo(a)pyrene 24.40 0.00 lndeno(1,2,3,c,d)pyrene+dibenz(a,h)anthracene >62.63 0.00 Benzo(g,h,i)perylene >31.38 0.00 GC=GAS CHROMATOGRAPH MDL= METHOD DETECTION LIMIT ZERO = NOT DETECTED 150 R03-5-1 14-Feb-03 20.44 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-5-2 14-Feb-03 73.18 3.53 22.49 0.00 5.20 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-5-3 14-Feb-03 266.89 961.85 120.57 4.08 17.90 0.00 7.87 3.60 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-5-5 14-Feb-03 467.45 983.88 113.38 11.43 29.00 3.65 18.23 8.96 5.81 7.17 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-6-1 14-Feb-03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ORGANIC GEOCHEMISTRY LABORATORY (tel. 519-888-45 Client: Christine Bishop c/o Roger Beckie UBC Laboratory Number: 030202 BTEX, PAH ANALYSIS Analysis occurred on Feb 19 to Feb 28, 2003 Analyst: Marianne VanderGriendt (x5180) Units are ug/L (micrograms per liter )(ppb) Field Duplicate Extraction duplicate Sample Identification MDL R03-6-2 R03-6-3 R03-6-3b R03-6-3b R03-6-4 14-Feb-03 14-Feb-03 14-Feb-03 14-Feb-03 14-Feb-03 Indane 2.98 27.38 71.13 72.28 69.52 285.86 Naphthalene 4.34 0.00 6.45 6.86 6.98 1755.83 Benzo(b)thiophene 6.63 0.00 18.92 21.64 22.10 140.49 lndole+2-Methyl naphthalene 4.66 0.00 0.00 0.00 0.00 10.45 1-Methyl naphthalene 2.68 0.00 8.74 8.41 9.79 45.96 Biphenyl 4.80 0.00 0.00 0.00 0.00 0.00 Acenaphthylene 2.67 0.00 0.00 0.00 0.00 9.42 Acenaphthene 2.27 0.00 0.00 0.00 0.00 14.25 Dibenzofuran 2.68 0.00 0.00 0.00 0.00 5.96 Fluorene 2.67 0.00 0.00 0.00 0.00 4.83 Phenanthrene 6.45 0.00 0.00 0.00 0.00 0.00 Anthracene 3.63 0.00 0.00 0.00 0.00 0.00 Carbazole >16.95 0.00 0.00 0.00 0.00 0.00 Fluoranthene 5.17 0.00 0.00 0.00 0.00 0.00 Pyrene 4.30 0.00 0.00 0.00 0.00 0.00 Benz(a)anthracene >15.69 0.00 0.00 0.00 0.00 0.00 Chrysene 6.30 0.00 0.00 0.00 0.00 0.00 Benzo(b+k)fluoranthene 20.11 0.00 0.00 0.00 0.00 0.00 Benzo(a)pyrene 24.40 0.00 0.00 0.00 0.00 0.00 lndeno(1,2,3,c,d)pyrene+dibenz(a,h)anthracene >62.63 0.00 0.00 0.00 0.00 0.00 Benzo(g,h,i)perylene >31.38 0.00 0.00 0.00 0.00 0.00 GC=GAS CHROMATOGRAPH MDL= METHOD DETECTION LIMIT ZERO = NOT DETECTED 151 ORGANIC GEOCHEMISTRY LABORATORY (tel. 519-888-45 Client: Christine Bishop c/o Roger Beckie UBC Laboratory Number: 030202 BTEX, PAH ANALYSIS Analysis occurred on Feb 19 to Feb 28, 2003 Analyst: Marianne VanderGriendt (x5180) Units are ug/L (micrograms per liter )(ppb) Sample Identification MDL R03-6-5 14-Feb-03 Indane 2.98 402.97 Naphthalene 4.34 938.46 Benzo(b)thiophene 6.63 100.53 lndole+2-Methyl naphthalene 4.66 5.63 1-Methyl naphthalene 2.68 41.45 Biphenyl 4.80 4.09 Acenaphthylene 2.67 21.14 Acenaphthene 2.27 10.16 Dibenzofuran 2.68 5.29 Fluorene 2.67 7.69 Phenanthrene 6.45 0.00 Anthracene 3.63 0.00 Carbazole >16.95 0.00 Fluoranthene 5.17 0.00 Pyrene 4.30 0.00 Benz(a)anthracene >15.69 0.00 Chrysene 6.30 0.00 Benzo(b+k)fluoranthene 20.11 0.00 Benzo(a)pyrene 24.40 0.00 lndeno(1,2,3,c,d)pyrene+dibenz(a,h)anthracene >62.63 0.00 Benzo(g,h,i)perylene >31.38 0.00 GC=GAS CHROMATOGRAPH MDL= METHOD DETECTION LIMIT ZERO = NOT DETECTED 152 R03-6-6 14-Feb-03 873.48 2008.42 136.29 4.03 15.04 7.15 9.76 6.72 8.64 16.03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-6-7 14-Feb-03 765.04 233.53 19.96 5.63 138.28 11.63 44.56 3.58 4.32 20.57 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-6-8 14-Feb-03 6.61 5.93 4.38 16.87 111.87 2.93 28.94 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-6-9 14-Feb-03 12.25 5.67 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ORGANIC GEOCHEMISTRY LABORATORY (tel. 519-888-45 Client: Christine Bishop c/o Roger Beckie UBC Laboratory Number: 030202 BTEX, PAH ANALYSIS Analysis occurred on Feb 19 to Feb 28, 2003 Analyst: Marianne VanderGriendt (x5180) Units are ug/L (micrograms per liter )(ppb) Sample Identification MDL Blank-1 19-Feb-03 Indane 2.98 0.00 Naphthalene 4.34 0.00 Benzo(b)thiophene 6.63 0.00 lndole+2-Methyl naphthalene 4.66 0.00 1-Methyl naphthalene 2.68 0.00 Biphenyl 4.80 0.00 Acenaphthylene 2.67 0.00 Acenaphthene 2.27 0.00 Dibenzofuran 2.68 0.00 Fluorene 2.67 0.00 Phenanthrene 6.45 0.00 Anthracene 3.63 0.00 Carbazole >16.95 0.00 Fluoranthene 5.17 0.00 Pyrene 4.30 0.00 Benz(a)anthracene >15.69 0.00 Chrysene 6.30 0.00 Benzo(b+k)fluoranthene 20.11 0.00 Benzo(a)pyrene 24.40 0.00 lndeno(1,2,3,c,d)pyrene+dibenz(a,h)anthracene >62.63 0.00 Benzo(g,h,i)perylene >31.38 0.00 GC=GAS CHROMATOGRAPH MDL= METHOD DETECTION LIMIT ZERO = NOT DETECTED 153 Blank-2 19-Feb-03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Blank-3 19-Feb-03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Blank-4 20-Feb-03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Blank-5 20-Feb-03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Blank-6 20-Feb-03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 ORGANIC GEOCHEMISTRY LABORATORY (tel. 519-888-45 Client: Christine Bishop c/o Roger Beckie UBC Laboratory Number: 030202 BTEX, PAH ANALYSIS Analysis occurred on Feb 19 to Feb 28, 2003 Analyst: Marianne VanderGriendt (x5180) Units are ug/L (micrograms per liter )(ppb) Sample Identification MDL R03-1-4 14-Feb-03 Indane 2.98 23.47 Naphthalene 4.34 5.02 Benzo(b)thiophene 6.63 4.81 lndole+2-Methyl naphthalene 4.66 16.16 1-Methyl naphthalene 2.68 2.87 Biphenyl 4.80 1.76 Acenaphthylene 2.67 19.00 Acenaphthene 2.27 0.00 Dibenzofuran 2.68 0.00 Fluorene 2.67 0.00 Phenanthrene 6.45 0.00 Anthracene 3.63 0.00 Carbazole >16.95 0.00 Fluoranthene 5.17 0.00 Pyrene 4.30 0.00 Benz(a)anthracene >15.69 0.00 Chrysene 6.30 0.00 Benzo(b+k)f I uoranthene 20.11 0.00 Benzo(a)pyrene 24.40 0.00 lndeno(1,2,3,c,d)pyrene+dibenz(a,h)anthracene >62.63 0.00 Benzo(g,h,i)perylene >31.38 0.00 GC=GAS CHROMATOGRAPH MDL= METHOD DETECTION LIMIT ZERO = NOT DETECTED 154 R03-2-3 14-Feb-03 413.78 11.01 55.10 12.10 6.47 0.00 26.43 3.16 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 GC duplicate R03-2-3 14-Feb-03 413.92 11.48 56.28 12.11 6.53 2.38 26.62 3.10 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-2-4 14-Feb-03 32.95 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 R03-3-5 14-Feb-03 315.03 22.62 37.44 12.39 1.85 0.00 40.25 2.85 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Blank-7 5-Mar-03 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 Appendix F: Geochemical Data February 2003 uM Anions 3 uS 3 uS 3 uS 3 uS 1uS 30 uS Sample Nitrate Phosphate Bromide Sulphate Acetate chloride R03-1-1 .0.9 ND ND 0.3 ND 103.9 R03-1-2 0.9 ND ND 0.3 15.2 248.5 R03-1-3 1.2. ND ND ND 10.3 243.8 R03-1-5 . 0.8 ND 21.9 0.01 ND 15669 R03-1-5B 0.7 ND 6.9 5 5.1 12135.2 R03-2-1 4.1 ND ND 3.1 ND 146.9 R03-2-2 0.8 ND ND 0.7 11.1 237.6 R03-2-3 1 ND 0.1 ND 7.3 177.1 R03-2-3B 0.8 ND 0.7 0.1 1.6 237.5 R03-1-4 1.5 ND 1.9 0.5 20.7 1222.6 R03-2-4 1 ND 0.1 1.2 31.3 133.4 R03-2-5 1.3 ND 36.1 0.4 6.4 17932 R03-3-1 1.2 ND 2.3 ND 8.6 652.1 R03-3-2 1.4 ND ND 0.2 ND 14.2 R03-3-3 1.2 ND ND 0.2 46.6 122.8 R03-3-4 1.8 ND ND 0.3 22.7 220.3 R03-3-4B 0.9 ND ND ND 20.1 80.9 R03-3-5 6.3 0.9 0.1 1.2 1.6 173.3 R03-3-6 1 ND 0.4 0.4 7.7 8472 R03-4-3 1.2 ND 0.1 0.1 46.6 162.9 R03-4-4 0.9 ND 0.1 18.2 39.2 206.5 R03-4-2 1.6 ND 0.1 0.1 16.5 118.2 R03-4-1 0.8 ND 1.6 ND 8.2 139.2 R03-4-5 0.9 ND ND ND ND 271.7 R03-4-6 1 ND ND 0.1 10.2 228.1 R03-5-1 0.8 ND 1.1 8.1 13.8 136.7 R03-5-2 0.9 ND 0.1 0.4 12.4 80.2 R03-5-3 2.6 ND ND ND 28.8 130.8 R03-5-3D 1.7 ND 0.9 ND ND 153.1 R03-5-5 1.4 ND 1.3 ND 0.3 10.3 R03-5-6 0.7 ND 0.7 ND 24.9 243.9 R03-6-2 0.7 ND 0.2 0.1 4.7 4.4 R03-6-3B 0.8 ND 1.2 0.2 8.6 224.3 R03-6-5 0.9 0.1 1 ND 27 193.5 R03-6-1 2.3 ND ND ND 14.6 183.1 R03-6-3 1.1 ND 0.2 ND 78 5.4 R03-6-4 1 ND 0.2 0.1 29 117.5 R03-6-6 0.7 ND ND ND 5.3 137.1 R03-6-7 1.5 ND ND 0.1 19.9 194.1 R03-6-8 1 ND 0.1 0.3 13.7 240.4 R03-6-9 1.7 ND 0.5 ND 34.7 232.1 ND=Not Detected AD=above detection (likely contamination) ?=technical difficulties during analysis S a m p l e J D Total Iron (mg/l) R03-6-1 76 R03-6-3 43 R03-6-5 69 R03-6-7 58 R03-6-9 38 R03-5-1 36 R03-5-3 52 R03-5-5 73 R03-4-1 95 R03-4-4 49 R03-4-5 72 R03-4-6 23 R03-3-2 41 R03-3-3 49 R03-3-4 55 R03-2-2 67 R03-2-3 55 R03-1-3 52 R03-1-4 23 Error from atmospheric contamination Peak Names Cone, in Cone, in Cone, in Cone, in Cone, in water water water water water error error error error error (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) (mg/L) Well CH4 C02 Ar 02 N2 CH4 C02 Ar 02 N2 R03-1-1 10.19 105.17 0.31 0.00 8.66 2.20 22.70 0.732 12.94 36.61 R03-1-3 12.83 78.37 0.38 0.00 6.66 0.70 4.26 0.153 2.71 7.66 R03-1-4 17.05 44.00 0.33 0.00 6.72 0.69 1.78 0.112 1.98 5.60 R03-1-5 21.82 90.01 0.27 0.00 4.97 3.72 15.34 0.552 9.74 27.50 R03-2-2 8.52 91.71 0.42 0.00 8.43 0.35 3.72 0.114 2.01 5.66 R03-2-3 15.04 67.30 0.37 0.00 7.04 0.54 2.41 0.100 1.76 4.98 R03-2-3b 13.84 72.89 0.33 0.00 5.30 0.72 3.80 0.143 2.52 7.19 R03-2-5 15.43 91.96 0.32 0.00 5.12 0.40 2.36 0.068 1.21 3.44 R03-3-2 8.03 102.61 0.41 0.00 8.11 0.36 4.55 0.121 2.14 6.10 R03-3-3 8.62 104.16 0.47 0.00 10.53 0.29 3.46 0.089 1.58 4.49 R03-3-4 13.46 85.16 0.29 0.00 4.81 0.43 2.70 0.086 1.51 4.31 R03-3-5 13.25 61.27 0.39 0.00 8.48 0.36 1.66 0.073 1.30 3.68 R03-3-6 18.22 67.69 0.28 0.00 5.35 0.95 3.54 0.146 2.57 7.30 R03-4-1 14.34 127.86 0.19 0.00 0.65 1.23 10.99 0.248 4.38 12.43 R03-4-2 7.36 84.45 0.38 0.00 5.68 0.33 3.79 0.121 2.14 6.10 R03-4-3 7.02 126.70 0.39 0.00 7.23 0.30 5.44 0.113 1.99 5.73 R03-4-4 12.86 87.73 0.27 0.00 3.61 0.42 2.87 0.084 1.48 4.28 R03-4-6 15.77 53.36 0.24 0.00 5.68 3.36 11.38 0.676 11.96 34.47 R03-5-1 5.62 118.20 0.41 0.00 8.53 0.26 5.41 0.122 2.17 6.20 R03-5-2 6.75 97.29 0.40 0.00 7.11 0.30 4.30 0.119 2.10 6.00 R03-5-3 13.72 94.07 0.31 0.00 5.73 0.36 2.50 0.070 1.23 3.52 R03-5-3b 12.88 88.13 0.28 0.00 4.15 0.50 3.45 0.105 1.85 5.30 R03-5-5 12.16 162.01 0.25 0.00 1.84 1.20 15.94 0.285 5.04 14.35 R03-5-6 10.45 96.60 0.33 0.00 5.98 0.81 7.49 0.220 3.89 11.06 R03-6-1 13.67 197.56 0.23 0.00 1.59 0.74 10.73 0.144 2.55 7.34 R03-6-2 5.68 99.14 0.37 0.00 6.40 0.36 6.29 0.170 3.01 8.66 R03-6-3 4.56 105.95 0.47 0.00 10.50 0.19 4.51 0.112 1.97 5.68 R03-6-3b 4.45 103.00 0.48 0.00 10.63 0.13 2.98 0.075 1.32 3.80 R03-6-4 6.35 88.20 0.42 0.00 7.74 0.20 2.80 0.082 1.46 4.19 R03-6-5 6.85 112.36 0.43 0.00 8.64 0.18 3.01 0.068 1.21 3.49 R03-6-6 6.88 159.80 0.40 0.00 8.87 0.18 4.13 0.065 1.15 3.34 R03-6-7 8.22 103.97 0.37 0.00 7.63 0.21 2.70 0.067 1.19 3.42 R03-6-8 8.61 36.63 0.34 0.00 6.36 0.32 1.35 0.097 1.71 4.92 R03-6-9 7.87 49.90 0.39 0.00 8.67 0.24 1.52 0.078 1.39 4.00 158 Cone, in water Cone, in water Predicted Well (mg/L) CH4 (mg/L) C02 C02 (mg/l) R03-1-1 10.19 105.17 R03-1-3 12.83 78.37 R03-1-4 17.05 44.00 R03-1-5 21.82 90.01 R03-2-2 8.52 91.71 212 R03-2-3 15.04 67.30 134 R03-2-3b 13.84 72.89 R03-2-5 15.43 91.96 192 R03-3-2 8.03 102.61 186 R03-3-3 8.62 104.16 189 R03-3-4 13.46 85.16 165 R03-3-5 13.25 61.27 139 R03-3-6 18.22 67.69 216 R03-4-1 14.34 127.86 726 R03-4-2 7.36 84.45 224 R03-4-3 7.02 126.70 216 R03-4-4 12.86 87.73 244 R03-4-6 15.77 53.36 103 R03-5-1 5.62 118.20 199 R03-5-2 6.75 97.29 165 R03-5-3 13.72 94.07 210 R03-5-3b 12.88 88.13 R03-5-5 12.16 162.01 246 R03-5-6 10.45 96.60 203 R03-6-1 13.67 197.56 1545 R03-6-2 5.68 99.14 328 R03-6-3 4.56 105.95 364 R03-6-3D 4.45 103.00 R03-6-4 6.35 88.20 241 R03-6-5 6.85 112.36 197 R03-6-6 6.88 159.80 284 R03-6-7 8.22 103.97 173 R03-6-8 8.61 36.63 79 R03-6-9 7.87 49.90 105 Sheetl Sample ID Depth (m) T(°C) pH Cond DO (MS) (mg/l) Acid Added (mL) Alkalinity(eq/L) Flask T (°C) Comments R03-1-1 6.3 5.6 * 177 1.7 6.80E-03 8 R03-1-2 8.2 5.5 * 244 1.4 5.60E-03 R03-1-3 10.04 5.4 * 212 0 1.1 4.40E-03 8 R03-1-4 12.26 5.3 * 466 0.3 1.37 5.48E-03 8 R03-1-5 13.68 5.4 * 1888 0.05 1.99 7.96E-03 7 Dup R03-2-1 8.3 4.4 * 408 1.67 6.68E-03 R03-2-2 10.39 5.1 6.57 255 0 1.54 6.16E-03 7 R03-2-3 12.73 6.7 6.47 219 0.8 3.20E-03 11 Dup R03-2-4 14.03 7.5 6.89 245 1.16 4.64E-03 R03-2-5 15.94 8.2 6.47 1675 0.1 1.19 4.76E-03 R03-3-1 4.43 8.9 6.24 608 3.44 1.38E-02 R03-3-2 7.37 7.6 6.61 229 1.44 5.76E-03 10 R03-3-3 9.32 7.7 6.63 230 0.3 1.47 5.88E-03 11 R03-3-4 11.03 9.1 6.56 218 0 1.32 5.28E-03 10 Dup R03-3-5 13.35 5.7 6.72 211 0.1 1.3 5.20E-03 9 R03-3-6 15.91 5.5 6.58 702 0.05 1.61 6.44E-03 R03-4-1 4.4 0.3 6.27 228 5 2.34 9.36E-03 9 R03-4-2 6.18 6.6 6.49 169 3 1.35 5.40E-03 12 R03-4-3 8.32 9.1 6.57 191 1 1.76 7.04E-03 15 Mild Creosote Odor R03-4-4 9.67 12 6.52 188 0 1.68 6.72E-03 17 Oily Film R03-4-5 11.64 14 6.49 192 0 1.45 5.80E-03 17 R03-4-6 13.16 10.1 6.78 170 0 1.34 5.36E-03 16 R03-5-1 5.3 10.9 6.49 172 0.1 1.33 5.32E-03 13 R03-5-2 8.15 9.7 6.58 182 0.05 1.36 5.44E-03 12 R03-5-3 9.58 10 6.54 180 0 1.38 5.52E-03 13 Dup R03-5-3b 12 R03-5-4 8.75 Biomarkers Only R03-5-5 11.57 5.6 6.47 157 2 1.45 5.80E-03 R03-5-6 13.89 4.9 6.55 165 0.8 1.48 5.92E-03 10 R03-6-1 3.66 3.8 5.9 235 0.3 2.19 8.76E-03 15 R03-6-2 5.75 9.2 6.28 166 0.1 1.32 5.28E-03 15 R03-6-3 7.48 11.4 6.23 187 0.3 1.23 4.92E-03 15 Biomarkers and Dup R03-6-4 8.9 11 6.39 154 0 1.27 5.08E-03 15 R03-6-5 10.2 11.4 6.51 175 0 1.32 5.28E-03 17 R03-6-6 12.16 13 6.39 188 0 1.58 6.32E-03 18 R03-6-7 13.36 10.8 6.58 189 0 1.44 5.76E-03 14 R03-6-8 15.03 10.7 6.86 175 0.1 1.32 5.28E-03 14 R03-6-9 16.05 10.8 6.88 205 0 1.78 7.12E-03 16 * = Technical Difficulties 160 Appendix G: Calibration of the Groundwater Flow Model G . l Introduction Calibration of the groundwater flow model at this site presented a challenge for two reasons. The tidally influenced hydrogeology at the site rendered instantaneous water level observations completely useless for calibration of a model that uses monthly time steps. The tracer plume at the site was observed to move over only a very small distance and therefore could constrain flow directions throughout the aquifer. In contrast, detailed hydrogeological information about the aquifer available from previous investigations (Golder, 1997, Golder, 1998, Anthony, 1998, Bianchin, 2001) provided good constraints on model input decreasing the necessity for strong calibration criteria. Continuous water level monitoring data was used to constrain gradients in the model and pump test data was used to assign hydraulic conductivity and storage. In addition, accurate pumping rates were obtained for the source containment wells at the site and input directly into the model. Because of the good constraints on model input, correlation of the model output to movement of the bromide tracer injected in February, 2000 and to fiowpaths indicated by distribution of the contaminant plume at the site required minimal adjustment. Because of the homogeneity in the aquifer observed in sediment sampling (this study, Anthony, 1998) the small region of the aquifer covered by the bromide tracer plume is considered to representative of the aquifer on the whole. G.2 Methodology The centre of mass of the bromide tracer plume was estimated from results presented in Bianchin (2001). This plume was observed to move southwest during the first 78 days it was monitored, thereafter the plume continued to move west at a low rate for the rest of the time it was monitored. The westward migration of the tracer plume indicates the influence of the river gradient on directions of groundwater flow. Slowing of the southern movement of the plume after the first 78 days of monitoring indicates lower aquifer gradients and a change in pumping rates after this period. 162 Hydraulic conductivity and storage values for the aquifer were assigned based on pumping test results. Aquifer gradients were adjusted within the range indicated by continuous water level monitoring data until the north south movement of the plume was consistent with movement of the tracer plume. The conductivity of the low conductivity zone adjacent to and underlying the river boundary was then adjusted so that fiowpaths indicated by particle tracking throughout the aquifer were consistent with the contaminant plume distributions observed. The east-west gradient along the river boundary was assigned based correlation with movement of the bromide tracer plume. G .3 Output Figure F l displays the movement of a particle released on the date of injection of the offshore tracer. The particle is observed to move south west for the first 70 days after release; thereafter it moves slightly north and then continues to move west up to 160 days. This is consistent with movement of the bromide tracer. Figure F2 displays the fiowpaths of particles released throughout the cross section. Particles released at the elevation of the plume core are observed to discharge approximately 70 metres offshore. This is consistent with profiling of the contaminant plume (Anthony, 1998, Bianchin, 2001). 163 * Data from Anthony(1998), Bianchin(2001), Lossor(2000) / -Injection [Point 2.5 5.0 / Meters The area in black outline in the upper window represents the area magnified in the bottom window. Arrows are spaced at 50 daytime intervals. Figure G . 1 Flowpath of a particle re leased from the offshore tracer injection point Prior to Pum ping 0,025 0.0 Under the influence of source containment 0.025 0.0 Kllom a (era Vertical Exaggerat ion = 4 Figure G .2 Part icle Tracking Resul ts in cross-sect ion 165 Appendix H: Geochemical Model Input Listing of M o d e l Input # S i m u l a t i o n w i t h minimum d e g r a d a t i o n r a t e o f n a p h t h a l e n e # D i s c u s s e d i n s e c t i o n 5.2.3 #No s o u r c e c o n t a i n m e n t w e l l # S i m u l a t i o n w i t h maximum d e g r a d a t i o n r a t e o f n a p h t h a l e n e # D i s c u s s e d i n s e c t i o n 5.2.3 #No s o u r c e c o n t a i n m e n t w e l l # S i m u l a t i o n w i t h minimum d e g r a d a t i o n r a t e o f n a p h t h a l e n e # D i s c u s s e d i n S e c t i o n 5.2.3 #Source c o n t a i n m e n t w e l l i s a c t i v e # S i m u l a t i o n w i t h maximum d e g r a d a t i o n r a t e o f n a p h t h a l e n e # D i s c u s s e d i n s e c t i o n 5.2.3 #Source c o n t a i n m e n t w e l l i s a c t i v e # S i m u l a t i o n d e g r a d a t i o n o f n a p h t h a l e n e by i r o n and meth #D e g r a d a t i o n o f O r g a n i c M a t t e r by Met h a n o g e n e s i s # D i s c u s s e d i n s e c t i o n 5.2.5 #Source c o n t a i n m e n t w e l l a c t i v e , maximum r a t e o f d e g r a d a t i o n # S i m u l a t i o n w i t h a l l d e g r a d a t i o n o f n a p h t h a l e n e by i r o n r e d u c t i o n # D i s c u s s e d i n s e c t i o n 5.2.6 # d e g r a d a t i o n o f o r g a n i c m a t t e r by methanogenesis {(Source c o n t a i n m e n t w e l l a c t i v e , maximum r a t e o f d e g r a d a t i o n # S i m u l a t i o n w i t h a l l d e g r a d a t i o n o f n a p h t h a l e n e by i r o n r e d u c t i o n # D i s c u s s e d i n s e c t i o n 5.2.7 # E q u i l i b r i u m w i t h S i d e r i t e and P y r i t e #Source c o n t a i n m e n t w e l l a c t i v e , maximum r a t e o f d e g r a d a t i o n # S i m u l a t i o n w i t h a l l d e g r a d a t i o n o f n a p h t h a l e n e by i r o n r e d u c t i o n # D i s c u s s e d i n s e c t i o n 5.2.8 #Surface c o m p l e x a t i o n #Source c o n t a i n m e n t w e l l a c t i v e , maximum r a t e o f d e g r a d a t i o n 4 < 167 # S i m u l a t i o n w i t h minimum d e g r a d a t i o n r a t e o f n a p h t h a l e n e #No s o u r c e c o n t a i n m e n t w e l l TITLE b a t c h _ r e a c t i o n SOLUTION MASTER SPECIES Naph Meth SOLUTION_ Naph l o g _ k Meth l o g _ k SOLUTION 1 temp pH pe re d o x u n i t s d e n s i t y Ca Fe (2) Fe(3) Naph Meth Naph Meth 0 0 128.18 16.042 128.18 16.042 SPECIES = Naph 0 Meth 0 14 6.2 0 pe mg/kgw 1 19 49 l e - 0 0 5 3 . 8 6 A l k a l i n i t y 0.00431 eq/kgw O(0) 0 S(6) 1. N(5) 0. -water 1 RATES Naph_methan - s t a r t as S042-kg Ks = qm = f l = r a t e moles 10 20 30 40 50 60 SAVE -end Naph - s t a r t 10 Ks = qm = f l = r a t e moles l e - 6 2.575e-13 MOL("Naph' = - q m * f l r a t e * MOLES i r o n r e d l e - 6 2.575e-13 MOL("Naph' = - q m * f l r a t e * )/(Ks+MOL("Naph")) TIME 20 30 40 50 60 SAVE MOLES -end KINETICS 1 Naph_methan - f o r m u l a -m -mO - t o l N a p h _ i r o n r e d - f o r m u l a -m -mO )/(Ks+MOL("Naph")) TIME Naph 1 Meth 0 . 0 0 . 0 le - 0 0 8 -6 C03-2 -4 H20 12 H Naph 100 . 0 100 . 0 1 H2 0 •38 C03-2 •10 OH- -76 Fe+2 -48 168 - t o l l e - 0 0 8 - s t e p s 34560000 i n 100 s t e p s # seconds - s t e p _ d i v i d e 1 - r u n g e _ k u t t a 3 SELECTED_OUTPTJT - f i l e - t o t a l s - m o l a l i t i e s M e l a n t e r i t e - s a t u r a t i o n _ i n d i c e s S i d e r i t e b a t c h . s e l Naph Ca Fe(2) Fe(3) HC03- Meth H e m a t i t e G o e t h i t e S i d e r i t e Fe(OH)3(a) S i d e r i t e H e m a t i t e G o e t h i t e - k i n e t i c r e a c t a n t s M e l a n t e r i t e N a p h _ i r o n r e d Naph_methan end 169 # S i m u l a t i o n w i t h maximum d e g r a d a t i o n r a t e o f n a p h t h a l e n e #No s o u r c e c o n t a i n m e n t w e l l TITLE b a t c h _ r e a c t i o n SOLUTION MASTER SPECIES 1 as S042-3 # kg Naph Naph Meth Meth SOLUTION_SPECIES Naph = Naph l o g _ k 0 Meth = Meth l o g _ k 0 SOLUTION 1 temp 14 pH 6.2 pe 0 re d o x pe u n i t s mg/kgw d e n s i t y 1 Ca 19 Fe(2) 4 9 Fe(3) l e - 0 0 5 Naph 3.8 Meth 6 A l k a l i n i t y 0.00431 eq/kgw 0(0) 0 S(6) 1. N(5) 0. -water 1 RATES Naph_methan - s t a r t 10 Ks = l e - 6 20 qm = 2 .575e-13 30 f l = MOL("Naph")/(Ks+MOL("Naph") ) 4 0 r a t e = - q m * f l 50 moles = r a t e * TIME 60 SAVE MOLES -end N a p h _ i r o n r e d - s t a r t 10 Ks = l e - 6 20 qm = 2 .575e-13 30 f l = MOL("Naph")/(Ks+MOL("Naph")) 4 0 r a t e = - q m * f l 50 moles = r a t e * TIME 60 SAVE MOLES -end KINETICS 1 Naph_methan - f o r m u l a Naph 1 Meth -6 C03-2 -m - m O - t o l N a p h _ i r o n r e d - f o r m u l a Naph 1 H2 0 -m 100.0 -mO 100.0 0 128.18 16.042 128.18 16.042 0 . 0 0 . 0 l e - 0 0 8 -4 H20 12 H -3 8 C03-2 -10 OH- -76 Fe+2 -48 170 - t o l le-008 -steps 34560000 i n 100 steps # seconds -step_divide 1 -runge_kut t a 3 SELECTED JDUTPUT - f i l e - t o t a l s - m o l a l i t i e s Melanterite -saturation_indices S i d e r i t e batch.sel Naph Ca Fe(2) Fe(3) HC03- Meth Hematite Goethite S i d e r i t e Fe(OH)3(a) S i d e r i t e Hematite Goethite - k i n e t i c reactants Melanterite Naph_ironred Naph_methan end 171 # S i m u l a t i o n w i t h mimimum d e g r a d a t i o n r a t e o f n a p h t h a l e n e #Source c o n t a i n m e n t w e l l i s a c t i v e TITLE b a t c h _ r e a c t i o n # SOLUTION_MASTER_SPECIES Naph Naph 0 128.18 Meth Meth 0 16.042 SOLUTION_SPECIES Naph = Naph l o g _ k 0 Meth = Meth l o g _ k 0 SOLUTION 1 temp pH pe re d o x u n i t s d e n s i t y Ca Fe (2) Fe(3) Naph Meth A l k a l i n i t y 128.18 16.042 14 6 . 2 0 pe mg/kgw 1 19 49 l e - 0 0 5 3 . 8 6 0.004 eg/kgw 0(0) 0 S(6) 1.1 N(5) 0.3 -water 1 # RATES Naph_methan - s t a r t as S042-kg l e - 6 2.575e-14 MOL("Naph")/(Ks+MOL("Naph")) TIME 10 Ks = 2 0 qm = 30 f l = 40 r a t e = - q m * f l 50 moles = r a t e * 60 SAVE MOLES -end N a p h _ i r o n r e d - s t a r t l e - 6 2 . 575e-14 MOL("Naph = - qm* f 1 r a t e * Ks = qm = f l = r a t e = moles 10 20 30 40 50 60 SAVE MOLES -end KINETICS 1 Naph_methan - f o r m u l a -m -mO - t o l N a p h _ i r o n r e d - f o r m u l a -m ')/(Ks+MOL("Naph")) TIME Naph 1 Meth -6 C03-2 0 . 0 0 . 0 le - 0 0 8 -4 H20 12 H Naph 100 . 0 1 H2 0 -38 C03-2 -10 OH- -76 Fe+2 -48 172 -mO - t o l - s t e p s - s t e p _ d i v i d e - r u n g e _ k u t t a 3 SELECTED_OUTPUT - f i l e - t o t a l s - m o l a l i t i e s M e l a n t e r i t e - a l k a l i n i t y - s a t u r a t i o n _ i n d i c e s S i d e r i t e 100 .0 l e - 0 0 8 120960000 i n 100 s t e p s # seconds 1 - k i n e t i c _ r e a c t a n t s -gases 02(g) C02(g) b a t c h . s e l Naph Ca Fe(2) HC03- Meth C03-2 Fe (3) H e m a t i t e G o e t h i t e S i d e r i t e f a l s e Fe(OH)3(a) M e l a n t e r i t e N a p h _ i r o n r e d S i d e r i t e H e m a t i t e G o e t h i t e Naph_methan end 173 # S i m u l a t i o n w i t h maximum d e g r a d a t i o n r a t e o f n a p h t h a l e n e #Source c o n t a i n m e n t w e l l i s a c t i v e TITLE b a t c h _ r e a c t i o n # SOLUTION MASTER SPECIES Naph Meth SOLUTION_ Naph = l o g _ k Meth = l o g _ k SOLUTION 1 temp pH pe r e d o x u n i t s d e n s i t y Ca Fe(2) Fe(3) Naph Meth Naph Meth 128 .18 16.042 128.18 16.042 SPECIES Naph 0 Meth 0 14 6.2 0 pe mg/kgw 1 19 49 l e - 0 0 5 3 . 8 6 A l k a l i n i t y 0.004 eq/kgw 0(0) 0 S(6) 1. N(5) 0. -water 1 RATES Naph_methan - s t a r t as S042-kg l e - 6 2 . 575e-13 MOL("Naph")/(Ks+MOL("Naph")) TIME 10 Ks = 2 0 qm = 30 f l 4 0 r a t e = - q m * f l 50 moles = r a t e 60 SAVE MOLES -end N a p h _ i r o n r e d - s t a r t l e - 6 2 . 575e-13 MOL("Naph")/(Ks+MOL("Naph" ) ) = - q m * f l r a t e * TIME Ks = qm = f l = r a t e = moles 10 20 30 40 50 60 SAVE MOLES -end KINETICS 1 Naph_methan - f o r m u l a -m - m O - t o l N a p h _ i r o n r e d - f o r m u l a -m Naph 1 Meth -6 C03-2 0 . 0 0 . 0 l e - 0 0 8 -4 H20 12 H Naph 100 . 0 1 H2 0 -3 8 C03-2 -10 OH- -76 Fe+2 -48 174 -mO - t o l - s t e p s - s t e p _ d i v i d e - r u n g e _ k u t t a 3 SELECTED_OUTPUT - f i l e - t o t a l s - m o l a l i t i e s M e l a n t e r i t e - a l k a l i n i t y - s a t u r a t i o n _ i n d i c e s S i d e r i t e 100 . 0 l e - 0 0 8 120960000 i n 100 s t e p s # seconds 1 - k i n e t i c _ r e a c t a n t s -gases 02(g) C02(g) b a t c h . s e l Naph Ca Fe(2) HC03- Meth C03-2 Fe (3) H e m a t i t e G o e t h i t e S i d e r i t e f a l s e Fe (OH) 3 (a) M e l a n t e r i t e N a p h _ i r o n r e d S i d e r i t e H e m a t i t e G o e t h i t e Naph_methan end 175 # S i m u l a t i o n d e g r a d a t i o n o f n a p h t h a l e n e by i r o n and meth # D e g r a d a t i o n o f O r g a n i c M a t t e r by Me t h a n o g e n e s i s # D i s c u s s e d i n s e c t i o n 5.2.5 #Source c o n t a i n m e n t w e l l a c t i v e , maximum r a t e o f d e g r a d a t i o n TITLE b a t c h _ r e a c t i o n # SOLUTION MASTER SPECIES Naph Naph Meth Meth SOLUTION SPECIES 128.18 16.042 128.18 16.042 Naph = Naph l o g _ k 0 Meth = Meth l o g _ k 0 TION 1 temp 14 pH 6 . 2 pe 0 r e d o x pe u n i t s mg/kgw d e n s i t y 1 Ca 19 Fe (2) 49 Fe (3) l e - 0 0 5 Naph 3 . 8 Meth 6 A l k a l i n i t y 0.004 0(0) 0 S(6) 1.1 as N(5) 0 . 3 -water 1 # kg RATES Naph_methan - s t a r t 10 Ks = l e - 6 20 qm = 2 .575e-13 30 f l 4 0 r a t e 50 moles = r a t e 60 SAVE MOLES -end N a p h _ i r o n r e d - s t a r t MOL("Naph")/(Ks+MOL("Naph")) = - q m * f l TIME l e - 6 2.575e-13 MOL("Naph")/(Ks+MOL("Naph")) = - q m * f l TIME 10 Ks = 2 0 qm = 30 f l = 40 r a t e 50 moles = r a t e 60 SAVE MOLES -end o c _ i r o n r e d - s t a r t 10 Ks=le-6 20 qm = 0.0e-14 30 f l = 1 4 0 r a t e = - q m * f l 50 moles = r a t e * TIME 176 60 SAVE MOLES -end oc_meth - s t a r t 10 Ks=le-6 2 0 qm = 3 . 0e-12 30 f l = 1 4 0 r a t e = - q m * f l 50 moles = r a t e * TIME 60 SAVE MOLES -end KINETICS 1 Naph_methan - f o r m u l a Naph 1 Meth -6 C03-2 -4 H20 12 H+ -8 -m 0.0 -mO 0.0 - t o l l e - 0 0 8 N a p h _ i r o n r e d - f o r m u l a Naph 1 H20 -38 C03-2 -10 OH- -76 Fe+2 -48 -m 100.0 -mO 100.0 - t o l l e - 0 0 8 o c _ i r o n r e d - f o r m u l a H+ 6 C03-2 -1 H20 -10 Fe2+ -4 -m 100.0 -mO 100.0 - t o l l e - 0 0 8 oc_meth - f o r m u l a Meth -1 C02 -1 -m 100.0 -mO 100.0 - t o l l e - 0 0 8 - s t e p s 120960000 i n 100 s t e p s # seconds - s t e p _ d i v i d e 1 - r u n g e _ k u t t a 3 SELECTED_OUTPUT - f i l e b a t c h . s e l - t o t a l s Naph Ca Fe(2) Fe(3) - m o l a l i t i e s HC03- Meth H e m a t i t e G o e t h i t e S i d e r i t e M e l a n t e r i t e - s a t u r a t i o n _ i n d i c e s Fe(OH)3(a) S i d e r i t e H e m a t i t e G o e t h i t e S i d e r i t e M e l a n t e r i t e - k i n e t i c _ r e a c t a n t s N a p h _ i r o n r e d Naph_methan end 177 # S i m u l a t i o n w i t h a l l d e g r a d a t i o n o f n a p h t h a l e n e by i r o n r e d u c t i o n # D i s c u s s e d i n s e c t i o n 5.2.6 # d e g r a d a t i o n o f o r g a n i c m a t t e r by methanogenesis #Source c o n t a i n m e n t w e l l a c t i v e , maximum r a t e o f d e g r a d a t i o n TITLE b a t c h _ r e a c t i o n # SOLUTION_MASTER_SPECIES Naph Naph 0 12 8.18 12 8.18 Meth Meth 0 16.042 16.042 SOLUTION_SPECIES Naph = Naph l o g _ k Meth l o g _ k SOLUTION 1 temp pH pe re d o x u n i t s d e n s i t y Ca Fe (2) Fe(3) Naph Meth 0 Meth 0 14 6 . 2 0 pe mg/kgw 1 19 49 l e - 0 0 5 3 . 8 6 A l k a l i n i t y 0.00431 eq/kgw 1 as S042-3 # kg 0(0) 0 S(6) 1. N(5) 0. -water 1 RATES Naph_methan - s t a r t 10 Ks = l e - 6 20 qm = 0.0e-13 30 f l = MOL("Naph")/(Ks+MOL("Naph")) 4 0 r a t e = - q m * f l 50 moles = r a t e * TIME 60 SAVE MOLES -end N a p h _ i r o n r e d - s t a r t 10 Ks = l e - 6 20 qm = 5.15e-13 30 f l = MOL("Naph")/(Ks+MOL("Naph") ) 4 0 r a t e = - q m * f l 50 moles = r a t e * TIME 60 SAVE MOLES -end o c _ i r o n r e d - s t a r t 10 Ks=le-6 2 0 qm = 0.0e-14 30 f l = 1 TIME TIME 1 H2 0 4 0 r a t e = - q m * f l 50 moles = r a t e * SO SAVE MOLES -end oc_meth - s t a r t 10 Ks=le-6 20 qm = 2.4e-12 30 f l = 1 40 r a t e = - q m * f l 50 moles = r a t e * 60 SAVE MOLES -end KINETICS 1 Naph_methan - f o r m u l a -m -mO - t o l N a p h _ i r o n r e d - f o r m u l a -m -mO - t o l o c _ i r o n r e d - f o r m u l a H+ 6 C03-2 -m 100.0 -mO 100.0 - t o l l e - 0 0 8 oc_meth - f o r m u l a Meth -1 -m -mO - t o l - s t e p s - s t e p _ d i v i d e - r u n g e _ k u t t a 3 SELECTED_OUTPUT - f i l e - t o t a l s - m o l a l i t i e s M e l a n t e r i t e - s a t u r a t i o n _ i n d i c e s S i d e r i t e Naph 0.0 0.0 le - 0 0 8 Naph 100 . 0 100 . 0 le - 0 0 8 1 Meth -6 C03-2 -4 H20 12 H+ -8 -38 C03-2 -10 OH- -76 Fe+2 -48 -1 H20 -10 Fe2+ C02 -1 100 . 0 100.0 l e - 0 0 8 120960000 i n 100 s t e p s # seconds 1 b a t c h . s e l Naph Ca Fe(2) Fe(3) HC03- Meth H e m a t i t e G o e t h i t e S i d e r i t e - k i n e t i c r e a c t a n t s Fe(OH)3(a) S i d e r i t e H e m a t i t e G o e t h i t e M e l a n t e r i t e N a p h _ i r o n r e d Naph_methan end 179 # S i m u l a t i o n w i t h a l l d e g r a d a t i o n o f n a p h t h a l e n e by i r o n r e d u c t i o n # D i s c u s s e d i n s e c t i o n 5.2.7 # E q u i l i b r i u m w i t h S i d e r i t e and P y r i t e #Source c o n t a i n m e n t w e l l a c t i v e , maximum r a t e o f d e g r a d a t i o n TITLE b a t c h _ r e a c t i o n # S OLUTION_MASTER_SPECIES Naph Naph 0 128.18 128.18 Meth Meth 0 16.042 16.042 SOLUTION_SPECIES Naph = Naph l o g _ k 0 Meth = Meth l o g _ k 0 EQUILIBRIUM_PHASES 1 S i d e r i t e ( d ) ( 3 ) P y r i t e SOLUTION 1 temp 14 pH 6.2 pe 0 r e d o x pe u n i t s mg/kgw d e n s i t y 1 Ca 19 Fe(2) 49 Fe (3) l e - 0 0 5 Naph 3 . 8 Meth 6 A l k a l i n i t y 0.004 0(0) 0 S(6) 1.1 as N(5) 0 . 3 -water 1 # kg RATES Naph_methan - s t a r t 10 Ks = l e - 6 20 qm = 0.0e-13 3 0 f l = MOL("Naph")/(Ks+MOL("Naph")) 4 0 r a t e = - q m * f l 50 moles = r a t e * TIME 60 SAVE MOLES -end N a p h _ i r o n r e d - s t a r t 10 Ks = l e - 6 20 qm = 5.15e-13 30 f l = MOL("Naph")/(Ks+MOL("Naph") ) 40 r a t e = - q m * f l 50 moles = r a t e * TIME 60 SAVE MOLES -end o c _ i r o n r e d - s t a r t 10 Ks=le-6 20 qm = 0.0e-14 TIME 1 H2 0 30 f l = 1 4 0 r a t e = - q m * f l 50 moles = r a t e * TIME 60 SAVE MOLES -end oc_meth - s t a r t 10 Ks=le-6 20 qm = 2 . 4e-12 30 f l = 1 4 0 r a t e = - q m * f l 50 moles = r a t e 60 SAVE MOLES -end KINETICS 1 Naph_methan - f o r m u l a -m -mO - t o l N a p h _ i r o n r e d - f o r m u l a -m -mO - t o l o c _ i r o n r e d - f o r m u l a H+ 6 C03 -m 100.0 -mO 100.0 - t o l l e - 0 0 8 oc_meth - f o r m u l a Meth -1 -m -mO - t o l - s t e p s - s t e p _ d i v i d e - r u n g e _ k u t t a SELECTED_OUTPUT - f i l e - t o t a l s - m o l a l i t i e s M e l a n t e r i t e - s a t u r a t i o n _ i n d i c e s S i d e r i t e Naph 0.0 0.0 le - 0 0 8 Naph 100 . 0 100 . 0 le - 0 0 8 1 Meth -6 C03-2 -4 H20 12 H+ -8 -38 C03-2 -10 OH- -76 Fe+2 -48 -1 H20 -10 Fe2+ C02 -1 100 . 0 100 . 0 le - 0 0 8 120960000 i n 100 s t e p s # seconds 1 3 b a t c h . s e l Naph Ca Fe(2) Fe(3) HC03- Meth H e m a t i t e G o e t h i t e S i d e r i t e - k i n e t i c r e a c t a n t s Fe(OH)3(a) S i d e r i t e H e m a t i t e G o e t h i t e M e l a n t e r i t e N a p h _ i r o n r e d Naph_methan end 181 # S i m u l a t i o n w i t h a l l d e g r a d a t i o n o f n a p h t h a l e n e by i r o n r e d u c t i o n # D i s c u s s e d i n s e c t i o n 5.2.8 #Surface c o m p l e x a t i o n #Source c o n t a i n m e n t w e l l a c t i v e , maximum r a t e o f d e g r a d a t i o n TITLE b a t c h _ r e a c t i o n # SOLUTION_MASTER_SPECIES Naph Naph 0 128.18 128.18 Meth Meth 0 16.042 16.042 SOLUTION_SPECIES Naph = Naph l o g _ k 0 Meth = Meth l o g _ k 0 SURFACE_SPECIES Hfo_sOH = Hfo_sOH l o g _ k 0.0 Hfo_sOH + H+ = Hfo_sOH2+ l o g _ k 7.2 9 # = p K a l , i n t Hfo_sOH = Hfo_sO- + H+ l o g _ k -8.93 # = - p K a 2 , i n t Hfo_sOH + Fe+2 = Hfo_sOFe+ + H+ l o g _ k 0.7 # LFER u s i n g t a b l e 10.5 Hfo_wOH = Hfo_wOH l o g _ k 0.0 Hfo_wOH + H+ = Hfo_wOH2+ l o g _ k 7.2 9 # = p K a l , i n t Hfo_wOH = Hfo_wO- + H+ l o g _ k -8.93 # = - p K a 2 , i n t Hfo_wOH + Fe+2 = Hfo_wOFe+ + H+ l o g _ k -2.98 Hfo_wOH + Fe+2 + H20 = Hfo_wOFeOH + 2H+ l o g _ k -11.55 Hfo_sOH + Ca+2 = Hfo_sOHCa+2 l o g _ k 4.97 Hfo_wOH + Ca+2 = Hfo_wOCa+ + H+ l o g _ k -5.85 SURFACE s o r p t i o n Hfo_wOH 6.4e-3 600 2.9 Hfo_sOH 1.5e-4 600 2.9 SOLUTION 1 temp 14 pH 6.2 pe 0 r e d o x pe u n i t s mg/kgw d e n s i t y 1 Ca 19 Fe(2) 49 Fe(3) l e - 0 0 5 Naph 3 . 8 Meth 6 A l k a l i n i t y 0.00431 eq/kgw 0(0) 0 S(6) 1.1 as S042-N(5) 0.3 -water 1 # kg RATES Naph_methan - s t a r t 10 Ks = l e - 6 20 qm = 0.0e-13 30 f l = MOL("Naph")/(Ks+MOL("Naph")) 4 0 r a t e = - q m * f l 50 moles = r a t e * TIME 60 SAVE MOLES -end N a p h _ i r o n r e d - s t a r t 10 Ks = l e - 6 20 qm = 5.15e-13 30 f l = MOL("Naph")/(Ks+MOL("Naph")) 40 r a t e = - q m * f l 50 moles = r a t e * TIME 60 SAVE MOLES -end o c _ i r o n r e d - s t a r t 10 Ks=le-6 20 qm = 0.0e-14 30 f l = 1 4 0 r a t e = - q m * f l 50 moles = r a t e * TIME 60 SAVE MOLES -end oc_meth - s t a r t 10 Ks=le-6 20 qm = 2.4e-12 30 f l = 1 40 r a t e = - q m * f l 50 moles = r a t e * TIME 60 SAVE MOLES -end KINETICS 1 Naph_methan - f o r m u l a Naph 1 Meth -6 C03-2 -4 H20 12 H+ -8 -m 0.0 -mO 0.0 - t o l l e - 0 0 8 N a p h _ i r o n r e d - f o r m u l a Naph 1 H20 -38 C03-2 -10 OH- -76 Fe+2 -48 -m 100.0 -mO 100.0 - t o l l e - 0 0 8 o c _ i r o n r e d - f o r m u l a H+ 6 C03-2 -1 H20 -10 Fe2+ -4 -m 100.0 -mO 100.0 - t o l l e - 0 0 8 oc meth - f o r m u l a Meth -1 C02 -1 -mO - t o l -m 100 . 0 100 . 0 le - 0 0 8 183 - s t e p s 120960000 i n 100 s t e p s # seconds - s t e p _ d i v i d e 1 - r u n g e _ k u t t a 3 SELECTED_OUTPUT - f i l e - t o t a l s - m o l a l i t i e s M e l a n t e r i t e - s a t u r a t i o n _ i n d i c e s S i d e r i t e b a t c h . s e l Naph Ca Fe(2) Fe(3) HC03- Meth H e m a t i t e G o e t h i t e S i d e r i t e Fe(OH)3(a) S i d e r i t e H e m a t i t e G o e t h i t e - k i n e t i c r e a c t a n t s M e l a n t e r i t e N a p h _ i r o n r e d Naph_methan end 184 Appendix I: Geochemical Model Output # S i m u l a t i o n w i t h m i n i m u m d e g r a d a t i o n # D i s c u s s e d i n s e c t i o n 5 . 2 . 3 #No s o u r c e c o n t a i n m e n t w e l l r a t e o f n a p h t h a l e n e PH O T Z ^ O — i i i n i » ' " M r H U H " 1 " " " D . Z 1 o one ft *> i R 1 D . I cJ3 c i n o. i y 6~4-fi<S— 1 1 1 1 1 1 1 -5000000 0 5000000 1000000 1500000 2000000 2500000 3000000 3500000 4000000 0 0 0 0 0 0 0 Time (s) Naphthalene Start (ug/l) 3798 Naphthalene Finish (ug/l) 3579 Naphthalene o -500000 0 5000000 1E+07 1.5E+07 2E+07 2.5E+07 3E+07 3.5E+07 4E+07 Time (s) 186 Initial Ferrous Iron (mg/l) Final Ferrous Iron (mg/l) 4 9 5 1 Iron to o 1.00E-003 7.00E-004 6.00E-004 15.00E-8G4-4TO0E-904-3.00E-004 2.00E-004 MryeE-904 Fe(2) Fe(3) -10000000 10000000 20000000 30000000 40000000 Time (s) Methane Start (mg/l) Methane Finish (mg/l) 6.00 6.08 Methane 3.8QE-e94-3.78E-004-g 3.77IE-004 o 3.76JE-G04 3.79E-004-3.74E-004-3.73E-004 • Methane -5E+0 6 5E+06 1E+07 2E+07 2E+07 3E+07 3E+07 4E+07 4E+07 Time (s) 187 # S i m u l a t i o n w i t h m a x i m u m d e g r a d a t i o n # D i s c u s s e d i n s e c t i o n 5 . 2 . 3 #No s o u r c e c o n t a i n m e n t w e l l r a t e o f n a p h t h a l e n e PH x o. -5000000 5000000 1000000 1500000 2000000 2500000 3000000 3500000 4000000 0 0 0 0 0 0 0 Time (s) Naphthalene Start (ug/l) Naphthalene Finish (ug/l) 3778 1627 Naphthalene ss. o 3.5QE-ee5-3. 2. 2. 1. )0E-0O5-5OE-O05-OOE-005-)0E-005-1.00E-005-0.00E+000 -500000 0 5000000 1E+07 1.5E+07 2E+07 2.5E+07 3E+07 3.5E+07 4E+07 Time (s) Initial Ferrous Iron (mg/l) Final Ferrous Iron (mg/l) 49 72 Iron o 1.40E-003 1.00E-003 6T00E-G04-4TO0E-004--2T00E-004-IO.OOEIOOO Fe(2) Fe(3) -10000000 10000000 20000000 30000000 40000000 Time (s) Methane Start (mg/l) Methane Finish (mg/l) 6 7 Methane 4.3QE-004-4.2OE-004-4.1OE-904-« 4.0qE-004 o S 3.9dE-004-3.8dE-004-3.7dE-004 • Methane -5E+0 6 5E+06 1E+07 2E+07 2E+07 3E+07 3E+07 4E+07 4E+07 Time (s) 189 # S i m u l a t i o n w i t h m i n i m u m d e g r a d a t i o n # D i s c u s s e d i n S e c t i o n 5 . 2 . 3 i S o u r c e c o n t a i n m e n t w e l l i s a c t i v e r a t e o f n a p h t h a l e n e PH r> oo X a UT^ U p n P O.Zo C OC D.ZD P 1/1 ft i*> ft OO e o-i O.Z 1 ft 1 i / o. i y -20000000 ( I 1 1 r i ^ i * D 20000000 40000000 60000000 80000000 10000000 12000000 14000000 0 0 0 Time (s) Naphthalene Start (ug/l) Naphthalene Finish (ug/l) 3792 3029 o S Sr5OE-05-3T00E-0J 2T50E-05-2T00E-05-1.50E-05 1.00E-05 5.00E-06 (D.OOEiOO -2000000 0 Naphthalene 20000000 40000000 60000000 80000000 1E+08 1.2E+08 1.4E+08 Time (s) 190 Initial Ferrous Iron (mg/l) Final Ferrous Iron (mg/l) 49 57 Iron 1.20E-03 1.J)0E-03 8. .Q>9E-re 6 o d)0E-e4-4.d)0E-04-2.f|0E-04 O.ODEiOO --2E+07 0 • Fe(2) • Fe(3) 2E+07 4E+07 6E+07 8E+07 1E+08 1E+08 1E+08 Time (s) Methane Start (mg/l) Methane Finish (mg/l) 6.00 6.29 Methane o -2E+07 2E+07 4E+07 6E+07 8E+07 Time (s) 1E+08 1.2E+08 1.4E+08 191 # S i m u l a t i o n w i t h m a x i m u m d e g r a d a t i o n # D i s c u s s e d i n s e c t i o n 5 . 2 . 3 # S o u r c e c o n t a i n m e n t w e l l i s a c t i v e r a t e o f n a p h t h a l e n e PH o o X CL C 0"7 O./tt C O^ O.ZO ft OE; ft Od c o o ft OO O.ZZ e o -i 0 . / 1 e o . O.Z 1 ft 1 O D. I y U, IU -20000000 ( ) 20000000 40000000 60000000 80000000 10000000 12000000 14000000 0 0 0 Time (s) Naphthalene Start (ug/l) Naphthalene Finish (ug/l) 3 7 9 2 3 0 2 9 Naphthalene SrSOE-es-o 3 T 0 0 E - 0 £ 2 T 5 0 E - 0 5 -2TO0E-05-5 0 E - 0 5 1 . 0 0 E - 0 5 B . 0 0 E - 0 6 O.OOEiOO - 2 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 6 0 0 0 0 0 0 0 8 0 0 0 0 0 0 0 1 E + 0 8 1 . 2 E + 0 8 1 . 4 E + 0 8 Time (s) 192 Initial Ferrous Iron (mg/l) Final Ferrous Iron (mg/l) 49 57 Iron 1 1.| OE-03 (DOE-8.(P0E-_ro o 6.i 4. 00E-04-OOE-04-2.d)0E-04-Fe(2) Fe(3) O.OPE 100 :. --2E+07 0 2E+07 4E+07 6E+07 8E+07 1E+08 1E+08 1E+08 Time (s) Methane Start (mg/l) Methane Finish (mg/l) 6.00 6.29 Methane 3^ 02E^ oT OT88E-04-3.86E-04 re o "i Q.Af=-f\A •78-2E-04-•T80E-04-•.78E-04 •T76E-04-3T74E-04 72E-04 -2E+07 2E+07 4E+07 6E+07 8E+07 Time (s) 1E+08 1.2E+08 1.4E+08 193 #Simulation degradation of naphthalene by i r o n and meth #Degradation of Organic Matter by Methanogenesis #Discussed i n s e c t i o n 5.2.5 ISource containment w e l l a c t i v e , maximum rate of degradation PH I Q. O.OD e c O.D (2 A O.OO p o D.O D . / O £ 4 C -20000000 ( 1 I I 1 1 I J 20000000 40000000 60000000 80000000 10000000 12000000 14000000 0 0 0 Time (s) Naphthalene Start (ug/l) Naphthalene Finish (ug/l) 3723 0 o 3 . 5 0 E ™ 0 5 3 T 0 0 E - 0 5 -2 T 5 0 E - G 5 -E T G 0 E - 0 5 -1.50E-05 1.00E-05 5 . 0 0 E - 0 6 0 : 0 Q E + 0 0 -2000000 0 Naphthalene 20000000 40000000 60000000 80000000 1E+08 1.2E+08 1.4E+08 Time (s) 194 Initial Ferrous Iron (mg/1) Final Ferrous Iron (mg/1) 49 89 Iron 80 E 03 o 2 4.fJ)0E-04-2.d)0E-04-O.0PDOO -2E+07 0 Fe(2) Fe(3) 2E+07 4E+07 6E+07 8E+07 1E+08 1E+08 1E+08 Time (s) Methane Start (mg/l) Methane Finish (mg/l) 6 13 Methane 9TOOE-Q4-JH o OlOOEiOO -2E+07 2E+07 4E+07 6E+07 8E+07 Time (s) 1E+08 1.2E+08 1.4E+08 195 # S i m u l a t i o n w i t h a l l d e g r a d a t i o n o f n a p h t h a l e n e b y i r o n r e d u c t i o n # D i s c u s s e d i n s e c t i o n 5 . 2 . 6 # d e g r a d a t i o n o f o r g a n i c m a t t e r b y m e t h a n o g e n e s i s t S o u r c e c o n t a i n m e n t w e l l a c t i v e , m a x i m u m r a t e o f d e g r a d a t i o n pH x Q. 1-7£— 7-A-7— o .y o o D.O C ~7 D. t c c D.O c c D.O C A D.4 c r> D.O e o A 6 r 4 - ! ! ! ! 1 -20000000 20000000 40000000 60000000 80000000 10000000 12000000 14000000 0 0 0 Time (s) Naphthalene Start (ug/l) Naphthalene Finish (ug/l) 3723 0 Naphthalene 3 T 0 0 E - 0 5 -2 T 5 0 E - 0 5 -o 2700E-05-1.50E-05 1.00E-05 B.00E-06 (D.OOEiOO -2000000 0 20000000 40000000 60000000 80000000 1E+08 1.2E+08 1.4E+08 Time (s) 196 Initial Ferrous Iron (mg/l) Final Ferrous Iron (mg/l) 49 128 Iron 2.50E-03 2.d)0E-03 1.S0E-03 o 5 1 .d)0E-03-5.(pOE-04 • Fe(2) Fe(3) O.OPE 100 rr-: J ^ I Z T T - r — ~ r: -2E+07 0 2E+07 4E+07 6E+07 8E+07 1E+08 1E+08 1E+08 Time (s) Methane Start (mg/l) Methane Finish (mg/l) 6.00 11.82 Methane 8T0OE-04-A n n P - D z o 3T0OE-04-0 0 E - 0 4 -OlOOEiOO -2E+07 0 2E+07 4E+07 6E+07 8E+07 1E+08 1.2E+08 1.4E+08 Time (s) 197 #Simulation with a l l degradation of naphthalene by i r o n r e d u c t i o n #Discussed i n s e c t i o n 5.2.7 #Equilibrium with S i d e r i t e and P y r i t e tSource containment w e l l a c t i v e , maximum rate of degradation PH r> A I Q. -200C <^ TT c on O.OO O.o p n c C? A C O.I 0 C A, D.l c nc f 0:UO 0000 ( i i i i i i i i 3 20000000 40000000 60000000 80000000 10000000 12000000 14000000 0 0 0 Time (s) Naphthalene Start (ug/l) 3723 Naphthalene Finish (ug/l) 0 Naphthalene Molality :+08 Molality •7o0t-U0 i -» cncr nc Molality n nnc nc Molality i.UUt-UO Molality 1 .out-uo A nnc nc Molality 1 .uut-uo c nnc ns Molality o.UUt-uo -2000000 ( 0 J 20000000 40000000 60000000 80000000 1E+08 1.2E+08 1.4E Time (s) 198 Initial Ferrous Iron (mg/l) Final Ferrous Iron (mg/l) 49 14 Iron 1.Q0E 03 9.d)0E-04 8.d)0E-04 7.00E-04 6.00E-04 JS 5.O0E-04-| 4.O0E-04-3.00E-04 2.d)0E-1 . 0 0 E - 0 4 -O . O O E i O O Fe(2) Fe(3) -2E+07 2E+07 4E+07 6E+07 8E+07 Time (s) 1E+08 1E+08 1E+08 Methane Start (mg/l) Methane Finish (mg/l) 6 12 Methane 8T©©E-G4-6.00E-04 -jo o 00E-04 JTOOE-04-^,00E-04 2T00E-04-r700E-04-00EI00 -2E+07 2E+07 4E+07 6E+07 8E+07 Time (s) 1E+08 1.2E+08 1.4E+08 199 # S i m u l a t i o n w i t h a l l d e g r a d a t i o n o f n a p h t h a l e n e b y i r o n r e d u c t i o n # D i s c u s s e d i n . s e c t i o n 5 . 2 . 8 # S u r f a c e c o m p l e x a t i o n t S o u r c e c o n t a i n m e n t w e l l a c t i v e , m a x i m u m r a t e o f d e g r a d a t i o n x a. -20000000 PH — C -T O.1c c D.O c c 0.0 C A 0.4 c o D.O c n A 6-4— > 20000000 40000000 60000000 80000000 10000000 12000000 14000000 0 0 0 Time (s) Naphthalene Start (ug/l) Naphthalene Finish (ug/l) 3 7 2 3 0 re o 3 T G 0 E - 0 5 -2 T 5 0 E - 0 5 -2 T 0 0 E - 0 5 -1 . 5 0 E - 0 5 1 . 0 0 E - 0 5 B . 0 0 E - 0 6 ( 5 . 0 0 E + 0 0 - 2 0 0 0 0 0 0 0 Naphthalene 2 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 6 0 0 0 0 0 0 0 8 0 0 0 0 0 0 0 1 E + 0 8 1 . 2 E + 0 8 1 . 4 E + 0 8 Time (s) 200 Initial Ferrous Iron (mg/l) Final Ferrous Iron (mg/l) 49 79 Iron J2 o Fe(2) Fe(3) O.OOEiOO -2E+07 0 2E+07 4E+07 6E+07 8E+07 1E+08 1E+08 1E+08 Time (s) Methane Start (mg/l) Methane Finish (mg/l) 6.00 10.65 Methane 7 .00E-04-6.iJGI 5 J ) 0 E - 0 4 r 4.0OE-O4 S 3.00E-04 2 .00E-04-1.60E-04-0.OQE+00 -2E+07 0 • Methane 2E+07 4E+07 6E+07 8E+07 1E+08 1E+08 1E+08 Time (s) t 

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